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1
Supporting Information for
Formation of Chlorobenzenes by Oxidative Thermal Decomposition
of 13-Dichloropropene httpdxdoiorg101016jcombustflame201502008
Nwakamma Ahubelema Kalpit Shaha Behdad Moghtaderia Mohammednoor Altarawnehab
Bogdan Z Dlugogorskiab Alister J Pagea
a Newcastle Institute for Energy and Resources The University of Newcastle Callaghan NSW
2308 Australia
b School of Engineering and Information Technology Murdoch University Murdoch WA 6150
Australia
2
Activation steps in the thermal decomposition of 13-Dichloropropene
C-Cl bond scission in 13-D (species R1 see Scheme S1) can take place at either the
vinylic or allylic carbons forming two distinct radicals IM1 and IM16 Computed reaction
enthalpies indicate that C-Cl fission from a vynilic site is barrierless and endothermic by
3713 kJmol Scission of the allylic C-Cl bond is the more favourable pathway being
endothermic by 2573 kJmol This follows since sp2-hybridized carbon exhibit more s
character than sp3-hybridized carbon and thus form shorter and stronger bonds An
alternative pathway to IM1IM16 formation is Cl abstraction from 13-D by ambient Cl
radicals (see Scheme S2) For the abstraction at the allylic carbon this pathway is
considerably more thermodynamically favourable (∆r Ηο298 = 801 kJmol) despite having
to overcome a barrier with ∆HDagger = 895 kJmol Abstraction of the vinyl chlorine is harder by
comparison (∆r Ηο298 = 1739 kJmol ∆HDagger = 2362 kJmol) but still requires less energy
than C-Cl bond scission Our relax scan confirms that scheme Cl abstraction by Cl gives a
genuine transition state Even though Cl prefers to abstract H with an activation enthalpy of
00 kJmol and exothermicity of -667 kJmol we propose that further formation of IM1 (after
initial decomposition by unimolecular C-Cl scission) would rather proceed via Cl abstracting
Cl due to comparatively lower reaction enthalpies In addition we found that HO2 abstracting
chlorine to form 13-D derived radicals require significantly higher reaction enthalpies than
Cl abstracting Cl (Scheme S3) However OH abstracting Cl and Cl abstracting Cl from 13-D
are thermodynamically competitive with each other Abstraction with OH also appears more
kinetically favourable This is in agreement with the findings of Wilk et al [1] who showed
that OH abstracting H from propene was found to be a more dominant reaction than HO2
abstraction reactions
3
Scheme S1 ∆r Ηο298 (kJmol) for (a) allylic C-Cl and (b) vinylic C-Cl bond scission in 13-
D
Scheme S2 ∆r Ηο298 (kJmol) for (a) allylic Cl and (b) vinylic Cl abstraction from 13-
dichloroprene by Cl
(a)
(b)
+Cl Cl CH2Cl
Cl
R1 IM1
25732785
+Cl Cl HCCl
Cl
R1 IM16
37733835
(a)
(b)
+ +Cl Cl Cl CH2Cl
Cl Cl
R1 IM1
TS1895923
801832
+ +Cl Cl Cl HCCl
Cl Cl
R1 IM16
TS223622350
17391848
4
Scheme S3 ∆r Ηο298 (kJmol) for allylic Cl ((a) and (c)) and vinylic Cl ((b) and (d))
abstraction from 13-dichloroprene by OH and OOH
Scission of the allylic and vinylic C-H bonds by comparison require significantly higher
energies than C-Cl bond scission (Scheme S4) Explicitly ∆r Ηο298 = 4497 kJmol (IM17
IM18) and 3397 kJmol (IM19) We therefore do not expect unimolecular C-H cleavage to
dominate during the initial decomposition of 13-D Similarly decomposition of 13-D via C-
C bond cleavage requires ∆r Ηο298 = 3990 kJmol (Scheme S5(a)) while C-C bond scission
of the 13-D-derived radical IM1 is barrierless but is highly endothermic with ∆r Ηο298 =
5862 kJmol (scheme S5(b))
+ +ClCl
OHCl
CH2 ClOH
+ +ClCl
OHCl
HC ClOH
+ +ClCl
HO
O ClCH2 Cl
O
OH
+ +ClCl
HO
OHC
Cl
ClO
OH
R1
R1
R1
R1
IM1
IM1
IM16
IM16
449749
16491799
14761744
26752794
584998
TS(a)
(b)
(c)
(d)
5
Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)
carbons
Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated
radical (b)
Cyclization of perchlorohexatrienes
Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)
The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4
initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23
While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713
(a)
(b)
(c)
+Cl Cl Cl ClCH
R1 IM17
44974475
+Cl ClC
Cl ClH
R1 IM18
44894479
+Cl ClCH
ClClH
R1 IM19
33973477
(a)
(b)
+Cl Cl CHClH2C
Cl
R1 IM20 IM21
39904175
+ClCH2
CHClCH2
IM1 IM20 IM22
58625717
6
kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form
IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)
However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then
formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is
exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol
Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-
elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the
formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was
produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules
out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15
has previously been observed in thermal decomposition experiments [4] However based on
the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =
264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation
of both IM15 and chlorobenzene (P1)
Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal
decomposition process These polychlorinated benzenes are potentially formed via successive
chlorination of monochlorobenzene at temperatures higher than 773 K This would require
either successive H abstraction by Cl atoms followed by addition of the latter to the vacant
radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In
either case the reaction enthalpies of these processes are favorable (for example 12-
dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)
and subsequent H elimination (∆r Ηο298 = 1052 kJmol))
Benzene was never observed in our combustion experiments and this can be attributed to
the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger
= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in
7
chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination
from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =
1158 kJmol Figure S2(c))
Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to
chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal
contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
-461-734
IM15
IM24
Cl
Cl
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
501395 473
358
IM25
25722491
P1+HCl
-1386-929
697792
Cl
ClH+
IM4IM23
8268
37134274
337264
236174
Cl
Cl
0
TS17
TS18
TS19
TS20
TS14
HCl
Cl
H
Cl
Cl
8
Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene
(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to
chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
An alternative pathway of polychlorinated benzenes is successive elimination of Cl from
hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has
been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was
not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy
surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low
levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash
1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene
hexachloropropene and hexachlorobutadiene The cyclization pathway for
Reaction coordinate
Rel
ativ
e en
thal
pyy
(kJ
mol
)
IM15
P1+HCl
-925-929
11581526
Cl
ClH+
0
TS14
(c)
HCl
Cl
H
P2+Cl2
26102610
IM26
120431
ClCl+
TS21
0
(a)
HCl
Cl
H
C
Cl
38003926
P1
+
P3+Cl
0
(b)
Cl
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
2
Activation steps in the thermal decomposition of 13-Dichloropropene
C-Cl bond scission in 13-D (species R1 see Scheme S1) can take place at either the
vinylic or allylic carbons forming two distinct radicals IM1 and IM16 Computed reaction
enthalpies indicate that C-Cl fission from a vynilic site is barrierless and endothermic by
3713 kJmol Scission of the allylic C-Cl bond is the more favourable pathway being
endothermic by 2573 kJmol This follows since sp2-hybridized carbon exhibit more s
character than sp3-hybridized carbon and thus form shorter and stronger bonds An
alternative pathway to IM1IM16 formation is Cl abstraction from 13-D by ambient Cl
radicals (see Scheme S2) For the abstraction at the allylic carbon this pathway is
considerably more thermodynamically favourable (∆r Ηο298 = 801 kJmol) despite having
to overcome a barrier with ∆HDagger = 895 kJmol Abstraction of the vinyl chlorine is harder by
comparison (∆r Ηο298 = 1739 kJmol ∆HDagger = 2362 kJmol) but still requires less energy
than C-Cl bond scission Our relax scan confirms that scheme Cl abstraction by Cl gives a
genuine transition state Even though Cl prefers to abstract H with an activation enthalpy of
00 kJmol and exothermicity of -667 kJmol we propose that further formation of IM1 (after
initial decomposition by unimolecular C-Cl scission) would rather proceed via Cl abstracting
Cl due to comparatively lower reaction enthalpies In addition we found that HO2 abstracting
chlorine to form 13-D derived radicals require significantly higher reaction enthalpies than
Cl abstracting Cl (Scheme S3) However OH abstracting Cl and Cl abstracting Cl from 13-D
are thermodynamically competitive with each other Abstraction with OH also appears more
kinetically favourable This is in agreement with the findings of Wilk et al [1] who showed
that OH abstracting H from propene was found to be a more dominant reaction than HO2
abstraction reactions
3
Scheme S1 ∆r Ηο298 (kJmol) for (a) allylic C-Cl and (b) vinylic C-Cl bond scission in 13-
D
Scheme S2 ∆r Ηο298 (kJmol) for (a) allylic Cl and (b) vinylic Cl abstraction from 13-
dichloroprene by Cl
(a)
(b)
+Cl Cl CH2Cl
Cl
R1 IM1
25732785
+Cl Cl HCCl
Cl
R1 IM16
37733835
(a)
(b)
+ +Cl Cl Cl CH2Cl
Cl Cl
R1 IM1
TS1895923
801832
+ +Cl Cl Cl HCCl
Cl Cl
R1 IM16
TS223622350
17391848
4
Scheme S3 ∆r Ηο298 (kJmol) for allylic Cl ((a) and (c)) and vinylic Cl ((b) and (d))
abstraction from 13-dichloroprene by OH and OOH
Scission of the allylic and vinylic C-H bonds by comparison require significantly higher
energies than C-Cl bond scission (Scheme S4) Explicitly ∆r Ηο298 = 4497 kJmol (IM17
IM18) and 3397 kJmol (IM19) We therefore do not expect unimolecular C-H cleavage to
dominate during the initial decomposition of 13-D Similarly decomposition of 13-D via C-
C bond cleavage requires ∆r Ηο298 = 3990 kJmol (Scheme S5(a)) while C-C bond scission
of the 13-D-derived radical IM1 is barrierless but is highly endothermic with ∆r Ηο298 =
5862 kJmol (scheme S5(b))
+ +ClCl
OHCl
CH2 ClOH
+ +ClCl
OHCl
HC ClOH
+ +ClCl
HO
O ClCH2 Cl
O
OH
+ +ClCl
HO
OHC
Cl
ClO
OH
R1
R1
R1
R1
IM1
IM1
IM16
IM16
449749
16491799
14761744
26752794
584998
TS(a)
(b)
(c)
(d)
5
Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)
carbons
Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated
radical (b)
Cyclization of perchlorohexatrienes
Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)
The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4
initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23
While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713
(a)
(b)
(c)
+Cl Cl Cl ClCH
R1 IM17
44974475
+Cl ClC
Cl ClH
R1 IM18
44894479
+Cl ClCH
ClClH
R1 IM19
33973477
(a)
(b)
+Cl Cl CHClH2C
Cl
R1 IM20 IM21
39904175
+ClCH2
CHClCH2
IM1 IM20 IM22
58625717
6
kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form
IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)
However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then
formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is
exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol
Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-
elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the
formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was
produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules
out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15
has previously been observed in thermal decomposition experiments [4] However based on
the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =
264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation
of both IM15 and chlorobenzene (P1)
Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal
decomposition process These polychlorinated benzenes are potentially formed via successive
chlorination of monochlorobenzene at temperatures higher than 773 K This would require
either successive H abstraction by Cl atoms followed by addition of the latter to the vacant
radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In
either case the reaction enthalpies of these processes are favorable (for example 12-
dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)
and subsequent H elimination (∆r Ηο298 = 1052 kJmol))
Benzene was never observed in our combustion experiments and this can be attributed to
the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger
= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in
7
chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination
from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =
1158 kJmol Figure S2(c))
Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to
chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal
contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
-461-734
IM15
IM24
Cl
Cl
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
501395 473
358
IM25
25722491
P1+HCl
-1386-929
697792
Cl
ClH+
IM4IM23
8268
37134274
337264
236174
Cl
Cl
0
TS17
TS18
TS19
TS20
TS14
HCl
Cl
H
Cl
Cl
8
Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene
(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to
chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
An alternative pathway of polychlorinated benzenes is successive elimination of Cl from
hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has
been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was
not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy
surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low
levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash
1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene
hexachloropropene and hexachlorobutadiene The cyclization pathway for
Reaction coordinate
Rel
ativ
e en
thal
pyy
(kJ
mol
)
IM15
P1+HCl
-925-929
11581526
Cl
ClH+
0
TS14
(c)
HCl
Cl
H
P2+Cl2
26102610
IM26
120431
ClCl+
TS21
0
(a)
HCl
Cl
H
C
Cl
38003926
P1
+
P3+Cl
0
(b)
Cl
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
3
Scheme S1 ∆r Ηο298 (kJmol) for (a) allylic C-Cl and (b) vinylic C-Cl bond scission in 13-
D
Scheme S2 ∆r Ηο298 (kJmol) for (a) allylic Cl and (b) vinylic Cl abstraction from 13-
dichloroprene by Cl
(a)
(b)
+Cl Cl CH2Cl
Cl
R1 IM1
25732785
+Cl Cl HCCl
Cl
R1 IM16
37733835
(a)
(b)
+ +Cl Cl Cl CH2Cl
Cl Cl
R1 IM1
TS1895923
801832
+ +Cl Cl Cl HCCl
Cl Cl
R1 IM16
TS223622350
17391848
4
Scheme S3 ∆r Ηο298 (kJmol) for allylic Cl ((a) and (c)) and vinylic Cl ((b) and (d))
abstraction from 13-dichloroprene by OH and OOH
Scission of the allylic and vinylic C-H bonds by comparison require significantly higher
energies than C-Cl bond scission (Scheme S4) Explicitly ∆r Ηο298 = 4497 kJmol (IM17
IM18) and 3397 kJmol (IM19) We therefore do not expect unimolecular C-H cleavage to
dominate during the initial decomposition of 13-D Similarly decomposition of 13-D via C-
C bond cleavage requires ∆r Ηο298 = 3990 kJmol (Scheme S5(a)) while C-C bond scission
of the 13-D-derived radical IM1 is barrierless but is highly endothermic with ∆r Ηο298 =
5862 kJmol (scheme S5(b))
+ +ClCl
OHCl
CH2 ClOH
+ +ClCl
OHCl
HC ClOH
+ +ClCl
HO
O ClCH2 Cl
O
OH
+ +ClCl
HO
OHC
Cl
ClO
OH
R1
R1
R1
R1
IM1
IM1
IM16
IM16
449749
16491799
14761744
26752794
584998
TS(a)
(b)
(c)
(d)
5
Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)
carbons
Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated
radical (b)
Cyclization of perchlorohexatrienes
Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)
The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4
initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23
While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713
(a)
(b)
(c)
+Cl Cl Cl ClCH
R1 IM17
44974475
+Cl ClC
Cl ClH
R1 IM18
44894479
+Cl ClCH
ClClH
R1 IM19
33973477
(a)
(b)
+Cl Cl CHClH2C
Cl
R1 IM20 IM21
39904175
+ClCH2
CHClCH2
IM1 IM20 IM22
58625717
6
kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form
IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)
However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then
formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is
exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol
Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-
elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the
formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was
produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules
out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15
has previously been observed in thermal decomposition experiments [4] However based on
the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =
264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation
of both IM15 and chlorobenzene (P1)
Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal
decomposition process These polychlorinated benzenes are potentially formed via successive
chlorination of monochlorobenzene at temperatures higher than 773 K This would require
either successive H abstraction by Cl atoms followed by addition of the latter to the vacant
radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In
either case the reaction enthalpies of these processes are favorable (for example 12-
dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)
and subsequent H elimination (∆r Ηο298 = 1052 kJmol))
Benzene was never observed in our combustion experiments and this can be attributed to
the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger
= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in
7
chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination
from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =
1158 kJmol Figure S2(c))
Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to
chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal
contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
-461-734
IM15
IM24
Cl
Cl
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
501395 473
358
IM25
25722491
P1+HCl
-1386-929
697792
Cl
ClH+
IM4IM23
8268
37134274
337264
236174
Cl
Cl
0
TS17
TS18
TS19
TS20
TS14
HCl
Cl
H
Cl
Cl
8
Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene
(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to
chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
An alternative pathway of polychlorinated benzenes is successive elimination of Cl from
hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has
been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was
not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy
surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low
levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash
1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene
hexachloropropene and hexachlorobutadiene The cyclization pathway for
Reaction coordinate
Rel
ativ
e en
thal
pyy
(kJ
mol
)
IM15
P1+HCl
-925-929
11581526
Cl
ClH+
0
TS14
(c)
HCl
Cl
H
P2+Cl2
26102610
IM26
120431
ClCl+
TS21
0
(a)
HCl
Cl
H
C
Cl
38003926
P1
+
P3+Cl
0
(b)
Cl
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
4
Scheme S3 ∆r Ηο298 (kJmol) for allylic Cl ((a) and (c)) and vinylic Cl ((b) and (d))
abstraction from 13-dichloroprene by OH and OOH
Scission of the allylic and vinylic C-H bonds by comparison require significantly higher
energies than C-Cl bond scission (Scheme S4) Explicitly ∆r Ηο298 = 4497 kJmol (IM17
IM18) and 3397 kJmol (IM19) We therefore do not expect unimolecular C-H cleavage to
dominate during the initial decomposition of 13-D Similarly decomposition of 13-D via C-
C bond cleavage requires ∆r Ηο298 = 3990 kJmol (Scheme S5(a)) while C-C bond scission
of the 13-D-derived radical IM1 is barrierless but is highly endothermic with ∆r Ηο298 =
5862 kJmol (scheme S5(b))
+ +ClCl
OHCl
CH2 ClOH
+ +ClCl
OHCl
HC ClOH
+ +ClCl
HO
O ClCH2 Cl
O
OH
+ +ClCl
HO
OHC
Cl
ClO
OH
R1
R1
R1
R1
IM1
IM1
IM16
IM16
449749
16491799
14761744
26752794
584998
TS(a)
(b)
(c)
(d)
5
Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)
carbons
Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated
radical (b)
Cyclization of perchlorohexatrienes
Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)
The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4
initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23
While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713
(a)
(b)
(c)
+Cl Cl Cl ClCH
R1 IM17
44974475
+Cl ClC
Cl ClH
R1 IM18
44894479
+Cl ClCH
ClClH
R1 IM19
33973477
(a)
(b)
+Cl Cl CHClH2C
Cl
R1 IM20 IM21
39904175
+ClCH2
CHClCH2
IM1 IM20 IM22
58625717
6
kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form
IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)
However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then
formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is
exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol
Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-
elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the
formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was
produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules
out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15
has previously been observed in thermal decomposition experiments [4] However based on
the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =
264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation
of both IM15 and chlorobenzene (P1)
Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal
decomposition process These polychlorinated benzenes are potentially formed via successive
chlorination of monochlorobenzene at temperatures higher than 773 K This would require
either successive H abstraction by Cl atoms followed by addition of the latter to the vacant
radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In
either case the reaction enthalpies of these processes are favorable (for example 12-
dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)
and subsequent H elimination (∆r Ηο298 = 1052 kJmol))
Benzene was never observed in our combustion experiments and this can be attributed to
the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger
= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in
7
chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination
from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =
1158 kJmol Figure S2(c))
Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to
chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal
contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
-461-734
IM15
IM24
Cl
Cl
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
501395 473
358
IM25
25722491
P1+HCl
-1386-929
697792
Cl
ClH+
IM4IM23
8268
37134274
337264
236174
Cl
Cl
0
TS17
TS18
TS19
TS20
TS14
HCl
Cl
H
Cl
Cl
8
Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene
(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to
chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
An alternative pathway of polychlorinated benzenes is successive elimination of Cl from
hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has
been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was
not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy
surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low
levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash
1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene
hexachloropropene and hexachlorobutadiene The cyclization pathway for
Reaction coordinate
Rel
ativ
e en
thal
pyy
(kJ
mol
)
IM15
P1+HCl
-925-929
11581526
Cl
ClH+
0
TS14
(c)
HCl
Cl
H
P2+Cl2
26102610
IM26
120431
ClCl+
TS21
0
(a)
HCl
Cl
H
C
Cl
38003926
P1
+
P3+Cl
0
(b)
Cl
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
5
Scheme S4 ∆r Ηο298 (kJmol) for C-H bond scission of 13-D at vinylic (a b) and allylic (c)
carbons
Scheme S5 ∆r Ηο298 (kJmol) for C-C bond scission of 13-D (a) and its dechlorinated
radical (b)
Cyclization of perchlorohexatrienes
Cyclisation of IM4 follows three successive steps to form dichlorocyclohexadiene (IM15)
The reactive potential energy surface of this process is given in Figure S1 Cyclisation of IM4
initiates with the rotation of the C(3)-C(4) C=C double bond to form the intermediate IM23
While only slightly endothermic the enthalpic barrier for this step is a prohibitive 3713
(a)
(b)
(c)
+Cl Cl Cl ClCH
R1 IM17
44974475
+Cl ClC
Cl ClH
R1 IM18
44894479
+Cl ClCH
ClClH
R1 IM19
33973477
(a)
(b)
+Cl Cl CHClH2C
Cl
R1 IM20 IM21
39904175
+ClCH2
CHClCH2
IM1 IM20 IM22
58625717
6
kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form
IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)
However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then
formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is
exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol
Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-
elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the
formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was
produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules
out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15
has previously been observed in thermal decomposition experiments [4] However based on
the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =
264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation
of both IM15 and chlorobenzene (P1)
Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal
decomposition process These polychlorinated benzenes are potentially formed via successive
chlorination of monochlorobenzene at temperatures higher than 773 K This would require
either successive H abstraction by Cl atoms followed by addition of the latter to the vacant
radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In
either case the reaction enthalpies of these processes are favorable (for example 12-
dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)
and subsequent H elimination (∆r Ηο298 = 1052 kJmol))
Benzene was never observed in our combustion experiments and this can be attributed to
the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger
= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in
7
chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination
from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =
1158 kJmol Figure S2(c))
Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to
chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal
contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
-461-734
IM15
IM24
Cl
Cl
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
501395 473
358
IM25
25722491
P1+HCl
-1386-929
697792
Cl
ClH+
IM4IM23
8268
37134274
337264
236174
Cl
Cl
0
TS17
TS18
TS19
TS20
TS14
HCl
Cl
H
Cl
Cl
8
Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene
(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to
chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
An alternative pathway of polychlorinated benzenes is successive elimination of Cl from
hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has
been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was
not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy
surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low
levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash
1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene
hexachloropropene and hexachlorobutadiene The cyclization pathway for
Reaction coordinate
Rel
ativ
e en
thal
pyy
(kJ
mol
)
IM15
P1+HCl
-925-929
11581526
Cl
ClH+
0
TS14
(c)
HCl
Cl
H
P2+Cl2
26102610
IM26
120431
ClCl+
TS21
0
(a)
HCl
Cl
H
C
Cl
38003926
P1
+
P3+Cl
0
(b)
Cl
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
6
kJmol Subsequent rotations of the C(2) bond to form IM24 and the C(5) bond to form
IM25 are significantly more kinetically favourable (∆HDagger = 337 501 kJmol respectively)
However both of these bond rotations are endothermic 12-dichlorocyclohexadiene is then
formed via disrotatory 6π electrocyclic ring closure (IM25 rarr IM15) This ring closure is
exothermic (∆r Ηο298 = -461) however is impeded by an activation enthalpy of 2572 kJmol
Chlorobenzene (P1) is formed from IM15 by a retro Diels-Alder rearrangement and syn-
elimination of HCl with a barrier of 697 kJmol Similar reactions have been observed in the
formation of benzene from 14-cyclohexadiene [2 3] Although chlorobenzene (P1) was
produced in significant yield during 13-D thermal decomposition Figure S1 effectively rules
out a closed-shell cyclisation pathway as a mechanism for its formation We note that IM15
has previously been observed in thermal decomposition experiments [4] However based on
the rate constant for the initial step in this cyclisation reaction at 873 K (IM4 rarr IM23 k =
264 times 10-12 s-1) it is unlikely that the pathway in Figure S1 is responsible for the formation
of both IM15 and chlorobenzene (P1)
Figures 2 and 3 show that di- to hexa-chlorobenzenes are formed during the thermal
decomposition process These polychlorinated benzenes are potentially formed via successive
chlorination of monochlorobenzene at temperatures higher than 773 K This would require
either successive H abstraction by Cl atoms followed by addition of the latter to the vacant
radical site on the phenyl ring or successive Cl addition followed by dehydrogenation In
either case the reaction enthalpies of these processes are favorable (for example 12-
dichlorobenzene can be formed via bullCl addition to chlorobenzene (∆r Ηο298 = -285 kJmol)
and subsequent H elimination (∆r Ηο298 = 1052 kJmol))
Benzene was never observed in our combustion experiments and this can be attributed to
the prohibitive kinetic barriers of Cl2 elimination from cis 16-dichlorocyclohexadiene (∆HDagger
= 2610 kJmol Figure S2(a)) and Cl reaction enthalpy required for Cl substitution in
7
chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination
from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =
1158 kJmol Figure S2(c))
Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to
chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal
contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
-461-734
IM15
IM24
Cl
Cl
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
501395 473
358
IM25
25722491
P1+HCl
-1386-929
697792
Cl
ClH+
IM4IM23
8268
37134274
337264
236174
Cl
Cl
0
TS17
TS18
TS19
TS20
TS14
HCl
Cl
H
Cl
Cl
8
Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene
(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to
chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
An alternative pathway of polychlorinated benzenes is successive elimination of Cl from
hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has
been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was
not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy
surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low
levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash
1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene
hexachloropropene and hexachlorobutadiene The cyclization pathway for
Reaction coordinate
Rel
ativ
e en
thal
pyy
(kJ
mol
)
IM15
P1+HCl
-925-929
11581526
Cl
ClH+
0
TS14
(c)
HCl
Cl
H
P2+Cl2
26102610
IM26
120431
ClCl+
TS21
0
(a)
HCl
Cl
H
C
Cl
38003926
P1
+
P3+Cl
0
(b)
Cl
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
7
chlorobenzene (∆r Ηο298 = 3926 kJmol Figure S2(b)) We note also that HCl elimination
from trans 16-dichlorocyclohexadiene is substantially more kinetically labile with (∆HDagger =
1158 kJmol Figure S2(c))
Figure S1 Cyclisation pathway for conversion of 16-dichlorohexatriene (IM4) to
chlorobenzene (P1) All values are given in kJmol and include zero-point energy and thermal
contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
-461-734
IM15
IM24
Cl
Cl
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
501395 473
358
IM25
25722491
P1+HCl
-1386-929
697792
Cl
ClH+
IM4IM23
8268
37134274
337264
236174
Cl
Cl
0
TS17
TS18
TS19
TS20
TS14
HCl
Cl
H
Cl
Cl
8
Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene
(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to
chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
An alternative pathway of polychlorinated benzenes is successive elimination of Cl from
hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has
been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was
not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy
surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low
levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash
1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene
hexachloropropene and hexachlorobutadiene The cyclization pathway for
Reaction coordinate
Rel
ativ
e en
thal
pyy
(kJ
mol
)
IM15
P1+HCl
-925-929
11581526
Cl
ClH+
0
TS14
(c)
HCl
Cl
H
P2+Cl2
26102610
IM26
120431
ClCl+
TS21
0
(a)
HCl
Cl
H
C
Cl
38003926
P1
+
P3+Cl
0
(b)
Cl
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
8
Figure S2 Reaction pathway for conversion of cis 16-dichlorocyclohexadiene to benzene
(P2)(a) Cl substitution in chlorobenzene (b) and trans 16-dichlorocyclohexadiene to
chlorobenzene (P1) (c) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
An alternative pathway of polychlorinated benzenes is successive elimination of Cl from
hexachlorobenzene Ring closure of octachlorohexatriene forming hexachlorobenzene has
been studied previously [4] however direct cyclisation of hexachloro-hexatriene itself was
not reported due to the absence of transition states on the B3LYP6-31G(2d) potential energy
surface The octachlorohexatriene precursor (IM27) was detected in our experiments at low
levels (not shown) during thermal decomposition of 13-D at higher temperatures (1023 ndash
1073 K) along with other polychlorinated unsaturated compounds such as tetrachloroethene
hexachloropropene and hexachlorobutadiene The cyclization pathway for
Reaction coordinate
Rel
ativ
e en
thal
pyy
(kJ
mol
)
IM15
P1+HCl
-925-929
11581526
Cl
ClH+
0
TS14
(c)
HCl
Cl
H
P2+Cl2
26102610
IM26
120431
ClCl+
TS21
0
(a)
HCl
Cl
H
C
Cl
38003926
P1
+
P3+Cl
0
(b)
Cl
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
9
hexachlorobenzene formation is shown in Figure S3 As for the formation of chlorobenzene
(Figure S1) this reaction mechanism is impeded by prohibitively high barriers The barrier
for the initial rotation in Figure S3 is smaller than that in Figure S1 whereas all others are
larger This is due to the increased electrostatic repulsion between individual Cl atoms which
actually changes the nature of the cyclisation pathway itself
Figure S3 Cyclisation pathway for conversion of hexachlorohexatriene (IM17) to
hexachlorobenzene (P4) All values are given in kJmol and include zero-point energy and
thermal contributions at 298 K G3MP2B3 results (top) M06-2X results (bottom)
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
25862696
TS25 2068
-357-647
IM31
IM29
Rel
ativ
e en
thal
py (k
Jm
ol)
Reaction coordinate
839841
1721
IM30
P4+Cl2
-726-540
+
IM27
IM28
17-13
5503
0
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
ClCl
Cl
Cl
Cl
Cl
Cl
Cl
ClCl
ClCl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl Cl
Cl
Cl
Cl
Cl
521545
25633256
TS22
TS23
TS24TS13
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
10
Figure S4 Transition state structures for cyclisation of 12-dichlorohexatriene forming
chlorobenzene
1787deg
12
34
TS17
12
34
TS18
1012deg
6
5
4
3
911deg
TS19 TS20
16
2550 Aring
1
6
1174 Aring
1992 Aring2585 Aring
TS21
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
11
Figure S5 Transition state structures for the cyclisation of octochlorohexatriene forming
hexachlorobenzene
1799deg
12
34
TS23
12
34
929deg
TS24
6
5
43
TS25
927deg
6 1
3026 Aring
TS26
TS27
1
6
3620 Aring2838 Aring
1905 Aring
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
12
Figure S6 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM5) forming chlorobenzene
1797deg
12
3
TS5
12
31014deg
TS6
TS76
5
4
3
914deg
TS8
16
44
1
6
2816 Aring
TS9
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
13
Figure S7 Transition state structures for the cyclisation of dichlorohexatriene-derived
radical(IM6) forming chlorobenzene
Table S1 Kinetic parameters of key cyclisation steps calculated for a temperature range
of 300-2000 K and pressure of 1 atm
Reaction Log A Ea (kJmol) T (K) k (s-1)
IM4rarrIM23 1431 4326 873 26 times10-12
IM5rarrIM7 1319 1763 873 4455
IM13rarrIM14 1071 38 873 30 times1010
00deg
1
2
34
TS11
TS12
6
5
4 3455deg
1
23
4
TS10
1658deg
16
TS13
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
14
Computational Kinetic and Thermodynamic Benchmarks
To provide a benchmark of accuracy of our computations we calculated the
thermodynamic parameters for the dehydrochlorination of ethyl chloride and the kinetic
parameters for the dehydrohalochlorination of ethyl chloride as well as the chlorine
abstraction reaction of ethylene and then compared the results with their respective
experimental values Table S2 compares the predicted and experimental standard enthalpy
change ∆Η298Κ for the dehydrochlorination of ethyl chloride while Table S3 compares the
calculated and experimental reaction rate parameters As illustrated our calculated
thermokinetic parameters remain in good agreement with the corresponding experimental
values For example the rate constant for the unimolecular decomposition of chloroethane
was determined experimentally as 158 s-1 at 7 atm and 1000 K [5] Our computational
calculations for the same conditions yield a conforming value of 244 s-1 Similarly the rate
of hydrogen abstraction (by chlorine atom) from ethylene amounts to 439times10-15
cm3molecules at 1 atm and 625 K [6] which corresponds to our calculated prediction of 105
times10-15 cm3molecules We have done similar benchmarking in our previous report [7] In
either case we find a good agreement between the experimental values and our calculated
data
Table S2 Comparison of calculated and experimental standard enthalpy change ∆Η298Κ
(kJmol) values for dehydrohalogenation of chloroethane
∆Η298Κ(kJmol) C2H5Cl rarrC2H4 + HCl 715 [8]a C2H5Cl rarrC2H4 + HCl 726 [8]a C2H5ClrarrC2H4 + HCl 729
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
15
Table S3 Experimental and calculated Arrhenius parameters for HCl elimination and
chlorine abstraction from acetylene and chloroethane
a Experimental value
T
(K) P
(atm) log A (s-1)
Ea (kJmol)
k
C2H5Clrarr C2H4+HCl
This work
1000 700 1379 2376 244 (s-1)
Ref [5]a 1384 2420
(plusmn484) 158 (s-1)
C2H5Clrarr C2H4+HCl
This work 772 016
1423 2350 214 times10-2 (s-1)
Ref [6]a 1400 2280 (plusmn831)
400 times10-2 (s-1)
C2H4+Clrarr C2H3+HCl
This work 625 100
-986 6126 105times10-15
(cm3molecules)
Ref [6]a -970 5571 439times10-15
(cm3molecules)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
16
Table S4 Percentage yield of products at 05 equivalence ratio and 10 s residence time products 673 K 723 K 773 K 823 K 873 K 923 K 973 K 1023 K 1073 K
13-dichloropropene 903526 742037 540637 533512 63691 05803 05713 05692 0
Chlorobenzene 0 0 00027 00950 00591 00633 00014 00024 0
12-dichlorobenzene 0 0 00132 00894 00851 00980 00222 00127 0
13-dichlorobenzene 0 0 00106 00788 00704 00979 00307 00152 0
14-dichlorobenzene 0 0 00154 00753 00753 00971 00347 00140 00033
123-trichlorobenzene 0 0 0 0 0 00109 00074 0 0
124-trichlorobenzene 0 0 0 0 0 00072 00077 00047 0
135-trichlorobenzene 0 0 00045 00078 00199 00641 00340 00079 0
1235-tetrachlorobenzene 0 0 0 0 0 0 00336 0 0
1234-tetrachlorobenzene 0 0 0 0 0 00080 00233 0 0
Pentachlorobenzene 0 0 0 0 0 0 00400 00053 0
Hexachlorobenzene 0 0 0 0 0 0 00061 00014 00003
Hexachlorobutadiene 0 0 0 0 0 0 0 00098 00087
Hexachloroethane 00131 00215 00121 00067 0 0 00000 0 0
2-chloronaphthalene 0 0 0 0 00167 00050 00053 00052 0
HCl 382 1189 2294 2315 4665 4948 4959 4968 4999
CO 006 168 459 486 1078 1060 1161 762 533
CO2 025 251 870 857 2633 2839 2845 3149 3400
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
17
Table S5 mz of selected products
Retention
time
Product Identified Ions (mz)
2768 13-dichloropropene 1099684 (6 ) 749998 (100 )
4016 Chlorobenzene 1120083 (100 ) 770380 (65 ) 510232 (15 )
6396 13-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6493 14-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
6859 12-dichlorobenzene 1459682 (100 ) 1109996 (35 ) 750230 (10 )
8369 124-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9053 135-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
9590 123-trichlorobenzene 1799294 (100 ) 1449601 (24 ) 1089601 (20 )
11218 1235-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
119 1234-tetrachlorobenzene 2158880 (100 ) 1809181 (10 ) 1449426 (8 ) 1079720 (10 )
13736 Pentachlorobenzene 2498482 (100 ) 2148799 (14 )
15981 Hexachlorobenzene 2838097 (100 ) 2488409 (275 )
9631 Hexachlorobutadiene 2598095 (40 ) 2248411 (100 ) 1898722 (40 )
7470 Hexachloroethane 2008407 (110 ) 1658723 (40 ) 1189030 (100 )
11873 2-chloronaphthalene 1620228 (100 ) 1270541 (20 )
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
18
Figure S8 Total Ion Chromatogram (TIC) of product species at 600 ˚C
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
19
Figure S9 Total Ion Chromatogram (TIC) of product species at 750 ˚C
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
20
Cartesian Coordinates (X Y Z) of the optimised TS in Angstrom (Aring)
TS1
X Y Z
C -150534100 128529000 005141700
H -157664100 235253600 -010499000
C -039541900 055233000 006083300
H -047868000 -052169400 020015300
C 093566300 114035700 -007635200
H 098845500 221794500 -021220800
C 206778900 041794500 -003144300
H 201238000 -065796300 010462100
C 338859600 101350700 -015124400
H 344023600 209084300 -028086200
C 455502400 036617800 -011500200
H 551165400 085932400 -020781300
Cl -340674200 029329500 024459100
Cl 469580900 -135066200 008008400
Cl -506408300 -100114000 -020280100
TS2
X Y Z
C -310964700 -092749500 041819300
C -198361900 -100546200 115211400
C -070892200 -055704000 070769400
C 050314700 -104639000 049559100
C 169083900 -026579500 017614600
C 286146100 -086394600 -003218900
H -407597700 -123549400 079280700
H -208494800 -135294600 217732000
H -078753700 081154200 047033400
H 062130300 -213141200 053436400
H 160162800 081376600 011732200
H 300608000 -193586100 001529900
Cl -313781600 -034262000 -119054300
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
21
Cl 430468500 000644100 -040589900
Cl -080217000 227895500 032510500
TS3
X Y Z
C 327788200 072540900 000402400
C 201936500 116649100 001819300
C 080317500 039771300 001976700
C -045664400 083530900 -000372500
C -163155500 -001877900 000889600
C -286447800 048492600 -001708300
H 412740300 139279100 000548400
H 189706900 225000500 003101100
H 087457900 -103812900 008399000
H -063147900 191369800 -003757000
H -148455000 -109312400 003890100
H -308048600 154516100 -004731200
Cl 372882200 -094364300 -001988700
Cl -428170400 -050440600 -000364000
H 080998900 -189998600 014503900
TS4
X Y Z
C 267617000 073450300 -002458900
H 288291700 179443000 002412100
C 148035300 015255500 -000006400
H 142550300 -093198300 -002534800
C 023488200 091706100 002653800
H 032047800 200085100 004914600
C -098072500 034457100 001387400
H -106350200 -073791900 -000901500
C -221461600 111334400 002280500
H -212776400 219607400 003928100
C -345459100 062019600 000978500
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
22
H -434032000 123857800 001592400
Cl 443530500 -050717200 -004423000
Cl -381436300 -107551800 -001335900
H 589785300 -194768700 059480900
TS5
X Y Z
C 171925900 052976800 020424500
C 046493100 010397900 -017694300
C -067799200 086326600 000007800
C -201630700 041209600 -041192600
C -288025000 -027031400 042975700
C -413311100 -070297200 008244200
H 191461400 148616400 066871700
H 037406400 -087738400 -063443000
H -058370700 184783700 045619700
H -234709200 063982600 -142361200
H -253551200 -048359100 144053500
H -473626500 -065582000 -081240900
Cl 312086600 -044541000 -002711300
TS6
X Y Z
C 135032500 029863900 -043055900
C 042064500 062911200 045310800
C -082320100 133957100 006281000
C -201202400 074681800 -008853500
C -224358200 -069262100 008098500
C -342181900 -126231900 -005379100
H 127633600 049917500 -149136900
H 057467000 038761700 150228500
H -075123200 241413100 -008058900
H -287351100 135163500 -035535600
H -137739500 -130522300 032829200
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
23
H -442478800 -093759400 -029208500
Cl 282081500 -051558600 001439500
TS7
X Y Z
C -092107200 -008415700 -016132000
C -038067800 107817700 019928600
C 103188500 146387200 010276900
C 210328400 071248600 -017363600
C 211403300 -075134200 -045444600
C 227888500 -165666800 047799900
H -038509600 -092773800 -056764400
H -104971900 183870700 058952000
H 121521600 251717600 029281300
H 307258100 120281700 -020432000
H 200687800 -106078800 -149635100
H 240948100 -165014800 155084200
Cl -262513900 -038201400 -000639900
TS8
X Y Z
C -072448300 018865300 -036503600
C -003180400 118847600 022459800
C 137941600 135559200 -001414000
C 225230500 032560200 -013565500
C 193799700 -107796500 010726700
C 073462000 -162723300 005715200
H -042844000 -026472700 -129921100
H -053051500 184015300 093520700
H 177843700 236497200 001359500
H 330284900 056393900 -026151600
H 278010900 -169269900 043244700
H 034109700 -261287200 026114300
Cl -238422600 -013632500 003960100
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
24
TS9
X Y Z
C -014612600 034858400 063080400
C -152290300 086188000 084227200
C -259999600 019995500 034745600
C -240503400 -101721300 -035218400
C -115369200 -161554600 -049249100
C -005900800 -103964200 011087400
H 057146100 050084400 144082900
H -162045000 183266800 131428300
H -359818400 060273300 045673700
H -327668400 -153112000 -074532500
H -107024200 -259102800 -095415000
H 088857500 -155080100 025363000
Cl 039657100 150666500 -067256400
Cl 286378600 -054733600 018512900
TS10
X Y Z
C 294240300 -051455600 006590500
C 195598300 036794300 -010624000
C 058095500 -001426100 -006539500
C -060099400 057441000 003006600
C -187092600 -013317300 -003683000
C -303726200 050002400 007355400
H 277498400 -156714300 025055400
H 219541000 141294600 -030350800
H -063909700 165728700 017838500
H -184640700 -120788100 -018281000
H -313107700 156789700 022189500
Cl 460873800 -006645900 001349900
Cl -456019500 -031856600 -000943300
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
25
TS11
X Y Z
C -211612400 -024548900 -000016000
C -196571800 108183100 -000007600
C -070887900 176621800 -000003800
C 060994000 165711300 000001800
C 137232700 041148900 -000014300
C 270470400 041134100 000015200
H -130618400 -096018800 -000029800
H -286049200 169963800 000005500
H 119735600 257536300 000023300
H 084390000 -053438900 -000050500
H 330417800 131250500 000052100
Cl -367678600 -099398400 000009400
Cl 364406500 -104060100 -000000600
TS12
X Y Z
C 164006100 -017451100 000110400
C 167060400 115474100 -012896300
C 052651100 201721000 -015060000
C -077121200 215670800 005011200
C -173153700 107567200 034152400
C -174591700 -006803800 -033417800
H 074001400 -076602200 008257000
H 264187600 163856300 -020247200
H -118699400 316396200 002489200
H -247697200 125336300 111135400
H -108978700 -027952200 -116879400
Cl 308750100 -111857100 008157500
Cl -286157200 -135090200 000539300
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
26
TS13
X Y Z
C 063617200 086558200 042630800
C -003813100 185017100 -039414200
C -134338900 193094400 -015717300
C -226913300 105124100 023654000
C -189587600 -033978000 008590400
C -064471800 -070843800 -041671600
H 036148100 071320500 146104700
H 045158900 221382200 -129303600
H -315020200 130217000 081491400
H -244468300 -106292300 067840100
H -027919900 -037471900 -137841000
Cl 229379300 049101900 008926200
Cl -003547100 -229630600 -002851200
TS14
X Y Z
C -061025500 033623100 -009020600
C -007394900 142708900 -088981700
C 122796800 178809600 -075924300
C 202052200 120748500 027069300
C 153594600 024355700 112570300
C 022814100 -021771600 097064500
H -044679000 -060651100 -077040100
H -072306800 187306000 -163401900
H 165802300 254231600 -140489800
H 304099600 155375300 039353400
H 215762100 -016810000 190925400
H -022330900 -089661500 168030100
Cl -234828900 039479000 025379300
Cl 049924800 -233634100 -048558200
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
27
TS15
X Y Z
C -212951000 016987700 046674200
H -200194000 019181800 154150200
C -137234000 091313900 -038637000
H -153952100 082364600 -145441000
C -035509700 175886000 008472200
H 009995600 247645900 -058332600
H -025198200 193909700 114753400
Cl 151151600 032325600 -002996000
Cl -335308600 -089201200 -007642900
Cl 342010900 -075373100 000980800
TS16
X Y Z
C -070711500 133438200 -030431100
H -014126600 208253200 -082134700
C -138806000 043401900 031777000
H -088813700 -044992800 071399500
C -287877700 054309600 053584800
H -309647400 050348200 160166000
H -328597000 145399700 010575900
Cl -370677100 -084619600 -022616400
Cl 183244300 041977300 -017009100
Cl 406583200 -060058000 010826000
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
28
TS17
X Y Z
C 314371200 -055058500 006480300
C 174503300 -077820200 045228600
C 081612900 -107405900 -042783900
C -059434200 -127675600 -005457500
C -153728000 -025549900 -015223500
C -287398600 -045371400 005813100
H 393297100 -123752300 034675600
H 145863200 -069240400 151748700
H 112011500 -116573500 -148454800
H -094035700 -229201900 012610800
H -119159800 074982800 -037669900
H -330848800 -142104500 027126400
Cl 369445300 106957600 -004570500
Cl -400426800 083582400 004312900
TS18
X Y Z
C 238739900 014228400 -041940800
C 161937900 075179800 047108300
C 069877800 185361800 009303400
C -061940800 170533500 -007910300
C -132772800 043834100 004984400
C -264508800 035675300 -012047500
H 239507000 038101800 -147497000
H 166986900 045024900 151496400
H 113501800 284159400 -002379300
H -121521100 257681500 -033597800
H -075662100 -045386800 028636000
H -327337500 120372800 -036459800
Cl 348649700 -113622800 000323200
Cl -352383500 -112779000 002195400
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
29
TS19
X Y Z
C -153624600 -021481200 -012312400
C -172097900 106608700 019404500
C -073456100 215143700 013365400
C 056998000 210312900 -015970800
C 134092800 088729900 -050598000
C 196238900 016439700 041352100
H -061075600 -065471200 -046138800
H -271395900 135718900 052167600
H -114455800 313075000 036099600
H 112204000 303927700 -016724200
H 140460200 059415000 -155272500
H 194461400 038955700 147184100
Cl -282747000 -136975500 -002000300
Cl 286917300 -126562300 002661500
TS20
X Y Z
C 123168000 002979400 032931000
C 143040300 112724300 -052768700
C 047456200 211321100 -054787700
C -047456600 211321500 054787200
C -143040300 112724300 052768700
C -123167400 002978800 -032930100
H 071708800 007237900 127314200
H 211999100 100273600 -135650400
H 022695300 258522000 -149493500
H -022696100 258523600 149492400
H -211999500 100274000 135650200
H -071707700 007237000 -127313100
Cl 223342700 -136951800 015690300
Cl -223342700 -136951900 -015690500
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
30
TS21
X Y Z
C 044844300 085837100 099176200
C 120173100 166084400 019380500
C 220840800 110031700 -062870000
C 249670600 -026286300 -062334800
C 177512600 -110787600 019325600
C 064092100 -059743700 095103100
H -034820000 124880900 161301400
H 102901200 272887900 017585900
H 278279100 175666400 -127282300
H 328940100 -065286300 -124809900
H 198917700 -216788500 024758000
H 040520000 -112329400 187216600
Cl -290988700 052866300 -024159200
Cl -072396000 -121680700 -022043900
TS22
X Y Z
C -288964700 009818900 -048734100
C -150811900 -026295000 -045384900
C -074573900 -016912200 065054700
C 064878000 -053997200 065470900
C 165769600 037798200 029995800
C 292649300 014056600 -015545300
Cl -409336000 -099548800 -001895600
Cl -080098900 -079908000 -196040800
Cl -145707800 037942400 214227300
Cl 094571300 -218484100 106593400
Cl 116154500 205440200 044444700
Cl 345558000 -139210200 -070042100
Cl -334732200 168695100 -085445600
Cl 410433500 137613500 -029790800
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
31
TS23
X Y Z
C 244213800 -043443400 -053526900
C 174116500 008958400 047034500
C 067988300 109387600 025790400
C -065119400 092231800 009235300
C -138883000 -036426900 009739500
C -271807800 -059811200 -001909900
Cl 204765900 -007438500 -217160500
Cl 213718100 -024018200 212126000
Cl 137209500 269003500 027494700
Cl -157730100 236554500 -016169900
Cl -040887900 -178889300 030798100
Cl -399242900 053935800 -020630500
Cl 373376100 -153712000 -031580000
Cl -334917500 -220458000 002288300
TS24
X Y Z
C -164476500 -132154600 -009089900
C -181510700 001883400 -001108800
C -085005800 117325300 -005822900
C 048398400 123473700 -027098600
C 148399400 017315200 -046564600
C 215559600 -036410800 055300300
Cl -018682500 -219524800 -030238100
Cl -348711500 049888000 015646000
Cl -160625800 272169700 020634200
Cl 129854800 277640000 -036538700
Cl 187907700 -018914400 -210932400
Cl 337957400 -154421300 035365400
Cl -297742300 -241705700 -000035400
Cl 176619500 002598300 218234700
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
32
TS25
X Y Z
C 105780400 077003400 -108192700
C 153141400 -036002000 -037626900
C 070413100 -134292800 015550500
C -070386900 -134311700 -015522700
C -153137800 -036026600 037629800
C -105801900 076995200 108184800
Cl 199332600 220222900 -116593700
Cl 315978000 -028728300 021010500
Cl 117852700 -228531400 151800400
Cl -117788000 -228564800 -151779200
Cl -315966400 -028786100 -021031700
Cl 019615000 070046100 224501000
Cl -019633300 070024800 -224508600
Cl -199393500 220187800 116593200
TS26
X Y Z
C 093290900 -017933100 -080981400
C 058638700 113902900 -067151800
C -071608700 147843200 -021812200
C -171001300 049719000 000383400
C -139822200 -083705000 -013056100
C 000948500 -124619700 -032229600
Cl 246211800 -063776700 -134307500
Cl 171407500 237402600 -103286900
Cl -109201400 310955800 003864900
Cl -330350400 097608100 043122200
Cl -257941300 -203910600 007010700
Cl 020268300 -278042500 -115241200
Cl 283526600 011358500 225614900
Cl 057097900 -141668200 149051400
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)
33
References 1 R D Wilk N P Cernansky W J Pitz C K Westbrook Combustion and Flame 77 (2) (1989) 145-170 2 U Bozkaya l l Oumlzkan The Journal of Physical Chemistry A 116 (12) (2012) 3274-3281 3 I Fleming E Wildsmith Journal of the Chemical Society D Chemical Communications (4) (1970) 223-224 4 H Detert D Lenoir H Zipse European Journal of Organic Chemistry 2009 (8) (2009) 1181-1190 5 P Evans T Ichimura E Tschuikow‐ Roux International Journal of Chemical Kinetics 10 (8) (1978) 855-869 6 J Manion R Huie R Levin VL Orkin W Tsang WS McGivern JW Hudgens VD Knyazev DB Atkinson E Chai AM Tereza C-Y Lin TC Allison WG Mallard F Westley JT Herron RF Hampson and DH Frizzell URL httpkineticsnistgov NIST Chemical Kinetics Database NIST Standard Reference Database 17) 20899-8320 7 N Ahubelem M Altarawneh B Z Dlugogorski Tetrahedron Letters 55 (35) (2014) 4860-4868 8 H Afeefy J Liebman S Stein NIST chemistry webbook NIST standard reference database 69 (2005)