School of Chemistry

CHY 8411 Final Report

ProjectTitle: Phosphido-Borane Stabilised Tetrylenes

Student Name: Alexander Craig

Supervisor: Dr Keith Izod

May 2016

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Contents1. Abstract………………………………………………………………………………………………………………………………………....32. Introduction…………………………………………………………………………………………………………………………………...4

2.1 Heteroatom Stabilised Tetrylenes…………………………………………………………………………………...42.2 Acyclic and Cyclic Dialkyl Stabilised Tetrylenes…………………………………………………………….....72.3 Phosphine-Borane Stabilised Tetrylenes………………………………………………………………………….8

3. Aims of the Project..............................................................................................................................114. Proposed Approach.............................................................................................................................125. Results & Discussion............................................................................................................................13

5.1 Synthesis and Characterisation of [Mes2P(BH3)]Li(THF)2....................................................135.2 Hydrolysis of [Mes2P(BH3)]Li(THF)2.....................................................................................155.3 Synthesis and Characterisation of [Mes2P(BH3)2]Li(THF)2..................................................165.4 Attempted Synthesis of [Mes2P(BH3)]2Sn...........................................................................185.5 Synthesis of [Dipp2P(BH3)]Li................................................................................................195.6 Attempted Synthesis of [Dipp2P(BH3)]2Sn..........................................................................205.7 Synthesis of [Ph2P(BH3)]Li...................................................................................................21

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5.8 Synthesis of [Ph2P(BH3)2]Li..................................................................................................225.9 Attempted Synthesis of [Ph2P(BH3)]2Sn..............................................................................235.10 Direct Synthesis and Characterisation of [(Ph2P(BH3))3Sn]Li(THF)2..................................245.11 Decomposition of [(Ph2P(BH3))3Sn]Li(THF)2......................................................................275.12 Synthesis of [Mes2P(BH3)CHPh]Li......................................................................................30

6. Conclusion...........................................................................................................................................317. Experimental.......................................................................................................................................338. References..........................................................................................................................................379. Acknowledgments..............................................................................................................................3910. Supplementary Material..................................................................................................................40

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Abstract

The phosphine Mes2PH, 24, (Mes = 2,4,6-trimethylphenyl), was prepared by the metathesis reaction

between PCl3 and MesMgBr, followed by hydride transfer with LiAlH4. The dimesitylphosphido-

borane lithium salt, [Mes2P(BH3)]Li(THF)2, 26, was successfully synthesised by boronation of 24 with

BH3.SMe2, and subsequent metalation with n-BuLi. The dimesitylphosphido-bis-(borane) lithium salt,

[Mes2P(BH3)2]Li(THF)2, 32, was successfully synthesised by metalation with n-BuLi, and subsequent

boronation, with two equivalents of BH3.SMe2, of 24. Both compounds were characterised by single

crystal X-ray diffraction (XRD). Analysis of the molecular structures of 26 and 32, confirms the

number of agostic-type interactions differs between the borane moieties and the coordinated

lithium cation.

The phosphine Ph2PH, 25, was prepared by the reduction of Ph3P with sodium, followed by

quenching with NH4Br. The diphenylphosphido-borane lithium salt, [Ph2P(BH3)]Li, 28, was

synthesised in situ by boronation of 25 with BH3.SMe2, followed by metalation with n-BuLi. The

attempted synthesis of the phosphido-borane stabilised stannylene, [(Ph2P(BH3))2]Sn, 40, by the

metathesis reaction between 28 and SnCl2, instead gave the phosphido-borane substituted stannate,

[(Ph2P(BH3))3Sn]Li(THF), 41, which was isolated and characterised by single crystal XRD. Compound

41 was then directly synthesised and characterised by 1H, 7Li, 11B, 31P and 119Sn NMR spectroscopy.

The molecular structure of 41 contains agostic-type interactions between the borane groups and the

lithium cation, but the interactions are absent between the borane groups and the low valent tin

centre. The tin centre is instead stabilised through a combination of steric and electronic effects

provided by the ligands.

The phosphine-borane stabilised carbanion complex, [Mes2P(BH3)CHPh]Li, 44, was prepared by the

metathesis reaction between 26 and PhCH2Br, followed by metalation with n-BuLi. 31P NMR

spectroscopy of the reaction mixture of 44 with stannocene, SnCp2, shows a signal indicative of a tin-

containing compound, but this compound was not isolated.

31P NMR spectroscopy revealed the attempted syntheses of [(Mes2P(BH3))2]Sn, 33, and

[(Dipp2P(BH3))2]Sn, 34, (Dipp = 2,6-diisopropylphenyl), were unsuccessful due to rapid decomposition

and hydrolysis of the products.

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ER'2N NR'2

ER'2P PR'2

ER'3C CR'3

ER'2C CR'2

R'

EC CP

R'2

P

R'2R'2 R'2

BH3 H3B

Introduction

Group 14 elements favour the formal +II and +IV oxidation states, with the +II oxidation state

becoming increasingly more favourable and accessible for the heavier elements. For example, Pb,

the heaviest element of group 14, the +IV oxidation state is highly unstable whereas the +II oxidation

state is readily accessible.1,2 In this regard, the +II oxidation state of the heavier group 14 elements

(Ge, Sn, Pb) is the state that is to be stabilised. To disfavour the dimerisation of various ligand

stabilised tetrylenes, E[R]2 where R = NR’2, PR’2, CR’3 , R’2C{P(BH3)R’2} (Figure 1), three principle ideas

need to be considered. Firstly, the use of amido (NR2) and phosphido (PR2) heteroatom ligands to

stabilise the low oxidation state metal centre,3-5 and a comparison of both heteroatom groups will be

discussed.6 The use of sterically bulky acyclic and cyclic hydrocarbyl ligands will follow,7-9 concluding

with the use of phosphido-borane ligands to stabilise the E(II) centre through agostic-type

interactions of the borane substituents and E. This is a new area of interest uncovered by Izod and

co-workers with promising results obtained in recent years.10-13

Figure 1. Generic structures of E[R]2, where R = NR’2, PR’2, CR’3, R’2C{P(BH3)R’2}.

Phosphido-borane stabilised tetrylenes [R2P(BH3)]2E, where E = Sn, Pb, are uncommon complexes

which is surprising because of the isoelectronic relationship phosphido-borane ligands share with

silyl ligands, [R3Si]-, and their use as key intermediates in a number of important reactions. 14-16 The

basis of the research is to isolate and deepen understanding of examples of this type.

Heteroatom Stabilised Tetrylenes

The chemistry involved with heavier group 14 metals and amido (NR2) ligands is comprehensive and

well developed. Diaminocarbenes [(R2N)2C] and their cyclic counterparts N-heterocyclic carbenes

have been widely studied since they were first isolated in 1991 by Arduengo.17 The stability of these

compounds can be attributed to the very efficient overlap of the heteroatom lone pairs with the

vacant pπ-orbital on the carbon. This mitigates the electron deficiency at carbon thereby stabilising

the singlet state relative to the triplet state. The efficient overlap causes the diaminocarbenes to be

strongly nucleophilic but only weakly electrophilic.

For diphosphinocarbenes and silylenes, [(R2P)2E], where E corresponds to C or Si respectively, there

is a decreased n-pπ-orbital overlap and thus significantly reduced stability. 18 Limited examples of

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SnP P

Ph

Armes2

Ph

Armes2

diphosphinocarbenes are available. A notable bulky example of [(R2P)ArC] where Ar = 2,4,6-

Me3C6H2.19

Compared to NR2 ligand species, PR2 ligands have been less extensively explored. One reason for this

is that there is a higher energetic barrier to inversion from the trigonal pyramidal configuration to

planar configuration, resulting in a stereo chemically active lone pair on phosphorus. This causes a

tendency to form oligomeric bridging arrangements when bound to metal centres. Earlier

comparison of phosphide ligands [P(SiMe3)2] to amido ligands [N(SiMe3)2] by Goel et al.2 and

Matchett et al.6 concluded that the phosphide ligands, 1-4, exhibit higher molecularities and

coordination numbers with inherently stronger bridge forming capabilities than the amido ligands

(Figure 2). This can be rationalised by the combination of the larger size and the lower

electronegativity of phosphorus versus nitrogen. If the phosphide ligands are sterically protected

they can offer advantageous electronic effects over amido ligands that can lead to novel low

coordinate metal centred monomeric systems with potentially unprecedented bonding schemes.

Figure 2. Structure of high molecularity [E{P(R)2}2]2 where E = Sn, ,Pb, R = SiMe3, tBu, 1-4.

Crystals were isolated of the novel, extremely bulky Sn(II)-diarylphosphide, [Ar mes2P(Ph)]2Sn, 5, by

Power et al.3 (Figure 3) that was monomeric in both solution and the solid state.

Figure 3. 5, where Armes2 = C6H3-2,6(C6H2-2,4,6-Me3).

Diaminogermylenes, [(R2N)2Ge], have been known since the 1970’s because of the ease of

accessibility of electron deficient Ge(II) metal centres from readily available starting materials, for

example GeI2 and GeCl2.(1,4-dioxane). Diphosphinogermylenes, [(R2P)2Ge], are far less well known as

the lone pair-pπ-orbital, n-pπ bonding interactions are likely to be very weak. Before 2005, there

was only one monomeric crystallographically characterised Ge(II) compound by Driess et al.4 but the

structural data was found to be too poor for detailed analysis.

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In 2005 Izod et al.5 isolated several novel Ge(II) complexes which included two unusual ‘ate’

complexes and an intramolecularly base-stabilised diphosphagermylene, [{(Me3Si)2CH}P(C6H4-2-

CH2NMe2)]2Ge, 6 (Equation 1).

Equation 1. Synthesis of 6 from the reaction of [{(Me3Si)2CH}P(C6H4-2-CH2NMe2)]K with 0.5 equivalents of GeI2.

Treatment of [{(Me3Si)2CH}P(C6H4-2-CH2NMe2)]K with 0.5 equivalents of GeI2 in THF gave the

intramolecularly base-stabilised diphosphagermylene, 6. The structure was established by X-ray

crystallography and elemental analysis. The Ge(II) centre is bound by one P atom and one N atom of

one of the phosphide ligands to form a six-membered chelate ring and is also bound by one P atom

of the second phosphide ligand. This arrangement gives a three-coordinate, trigonal pyramidal Ge

metal centre with a stereo chemically active lone pair. The N atom on the second ligand was shown

to not have any contacts with Ge. The Ge-P bond lengths were comparable to the Ge-P lengths

reported for [(R2P)2Ge(II)]. Both P atoms are distinctly pyramidal, which suggests that there is poor n-

pπ-orbital overlap, consistent with an intramolecular base stabilised Ge(II) centre. The monomer is

chiral at the two P atoms and also at Ge.

When [{(Me3Si)2CH}P(C6H4-2-CH2NMe2)]Li is treated with 0.5 equivalents of GeI2, the novel ‘ate’

complex [{(Me3Si)2CH}P(C6H4-2-CH2NMe2)]2GeLi2I2(OEt2)3 was formed, as confirmed by X-ray

crystallography. The terminal N atom is bound to the Li2I2 fragment but as the coordination

geometry of the Ge(II) centre is very similar to 6, the fact that the Li2I2 is bound has little significance.

Izod et al.20 reported the synthesis of a relatively bulky phosphide ligand, {(Me3Si)2CH}(Ph)PH, 7, the

preparation of its lithium, 8, sodium and potassium derivatives, and with the reaction of these

derivatives with ECl2, where E = Ge, Sn, the formation of either diphosphatetrylenes or ‘ate’

complexes.

Scheme 1. Synthesis of 9 from the reaction of the prepared ligand, 8, with SnCl2.

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Reaction of 8 with SnCl2 yields the ate complex, [{(Me3Si)2CH}(Ph)P]3SnLi(THF), 9, unexpectedly,

irrespective of the reaction stoichiometry (it would only be expected with a 3:1 ratio of 8:SnCl2)

(Scheme 1). The expected homoleptic complex [{(Me3Si)2CH}(Ph)P]2Sn is not observed even at 0.5

equivalents of SnCl2.

Similarly the reaction of GeCl2(1,4-dioxane) with 3 equivalents of 8 yields the Ge analogue, 10. Both

9 and 10 retain their structure in toluene but form their respective separated ion pair complexes on

crystallisation from hexanes/THF.

Single crystals of 10 suitable for X-ray crystallography were isolated from cold hexanes/THF which

showed that at each P atom was a chiral centre. The three P atoms form μ-bridges between the Li

and Ge centres creating a trigonal bipyramidal GeP3Li core with a trigonal pyramidal geometry at Ge.

Acyclic and Cyclic Dialkyl Stabilised TetrylenesDialkyltetrylenes are limited to only a few examples in the literature. Alkyl ligands principally provide

kinetic stabilisation to group 14 tetrylenes by sterically hindering the electron deficient E(II) centre,

preventing attack from nucleophilic species.21 There is no thermodynamic stabilisation because of

the lack of electronegative heteroatoms available to stabilise the sp2 lone pair in the singlet state. In

recent years, there have been numerous reports of diarylstannylenes but only very few cases of

dialkylstannylenes.7-9,22,23 The former generally allows for increased steric hindrance of the heavier

tetrylenes therefore decreasing the tendency to dimerise further than for dialkylstannylenes.

Lappert et al.7 in 1973 reported the archetypal dialkylstannylene, Sn[CH(SiMe3)2]2, 11, which is

monomeric in benzene solution but favours dimerisation in the solid state because of the lack of

steric bulk around the Sn(II) centre (Figure 4). The dimer was also the first time formal multiple

bonding was observed between the heavier main group elements, row 3 and heavier.

Figure 4. Dimerisation of 11 in benzene.

The first dialkylstannylene to be shown categorically to be a monomer in the solid state,

{(Me3Si)2CCH2}2Sn, 12, was isolated by Kira et al.8 (Figure 5) in 1991 as 12 provides sufficient steric

bulk to disfavour dimerisation.

The only other monomeric dialkylstannylene, {(Me3Si)2C(SiMe2CH2)}2Sn, 13, that has been fully

structurally characterised and isolated was by Eaborn et al.9 in 2000 (Figure 6).

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The dialkylplumbylene analogue, {(Me3Si)2C(SiMe2CH2)}2Pb, 14, was also characterised by Eaborn et

al. in 1997,22 becoming the first dialkyllead species to be isolated. Both 13 and 14 are composed of a

sterically bulky seven-membered ring surrounding the E(II) centre. Jutzi et al.23 in 1991 were able to

characterise the first unsymmetrically substituted acyclic dialkylgermylene, (Me3Si)3CGeCH(SiMe3)2,

15, in the solid state (Figure 7). The molecule has similarities to that of 13 with the exception of

having three SiMe3 substituents on one of the alkyl ligands. This creates enough steric bulk to

disfavour dimerisation of the monomer.

Figures 5, 6 and 7. 12, 13 and 15 isolated by Kira, Eaborn and Jutzi et al. respectively.

Phosphine-Borane Stabilised TetrylenesPhosphine-borane substituted carbanion ligand systems, [R2P(BH3)CR’2]- have been shown to

stabilise low valent tetrylene compounds through agostic-type interactions.11,12,13 Significant

interactions between the vacant 5pπ- and 6pπ-orbitals in Sn and Pb respectively, and the B-H σ-

orbitals of the ligand have been observed. Substantial delocalisation of the B-H σ-bonding electron

density into the vacant 5pπ-orbital of Sn and the 6pπ-orbital of Pb stabilise the low valent tetrylene

centres.

Given the relatively straightforward synthesis of phosphido-borane ligands, [R 2P(BH3)]-, and their

potential utility it’s surprising they have received very little attention. Phosphido-boranes have been

noted to be key intermediates in the synthesis of chiral phosphines and are used in the catalytic

dehydrocoupling to give polymeric materials.15 They have also been shown to be precatalysts for the

formation of P-C sp bonds when bound to Cu(I).16 In these applications the intermediates are usually

generated in situ with very few being isolated and characterised in the solid state. The isolated

examples are bound as monomers, dimers or polymers to Li, Na or K metals.

As noted earlier, [R2P(BH3)]- ligands are isoelectronic with [R3Si]-. Izod et al.10 reacted [{nPr2P(BH3)}

(Me3Si)CCH2][Li(THF)2]2 with SnCl2 in THF to produce the novel dialkylstannylene, [{nPr2P(BH3)}

(Me3Si)CCH2]2Sn, 16, as air sensitive yellow crystals (Figure 8). It was noted the similarity of this

compound with that of 12. 16 was prepared in excellent yield after a simple work-up whereas 12

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was only isolated in low yields after a difficult work-up. This can be attributed to the increased

charge delocalisation away from the carbanion in the ligand used to produce 16 than for the ligand

used to produce 12 due to the increasing charge delocalising ability of phosphine-borane ligands

versus silyl ligands. This therefore makes the dicarbanion less nucleophilic, causing a decreased

tendency to reduce Sn(II) to Sn(0). If heated to 60 ° in hexanes or left in light for a week, 16 will

decompose to elemental tin and the phosphine-borane alkyl ligand.

Figure 8. 16 isolated by Izod et al.1H, 11B{1H}, 31P{1H} and 119Sn NMR spectra of 16 shows that it is a 1:1 mixture of the two possible

diastereoisomers. Pure rac-16 or meso-16 isomers can be obtained by selective crystallisations. The

X-ray crystal structures of both diastereoisomers of 16 show short agostic-type B-H…Sn contacts, not

seen before for dialkylstannylene compounds but reported for a few cases of the transition metals.

Rac-16 has one interaction either side of the five-membered ring with one H atom from each BH 3

group in close proximity to that of the electron-deficient Sn(II). The meso- isomer has both BH3

substituents on the same side of the heterocycle but only one short B-H…Sn contact is observed,

although it is significantly shorter than the corresponding distances in rac-16; well within the sum of

the Van der Waal radii of Sn and H atoms.

Compound 16 was the first example of a B-H…E interaction that involved a low oxidation main group

metal centre and these interactions mitigate the electron deficiency of the Sn(II) centre allowing the

monomeric form to persist in solution.

The Pb analogue, [{nPr2P(BH3)}(Me3Si)CCH2]2Pb, 17, was also characterised in 2008 by Izod et al.11 to

extend the general principles of the phenomenon of agostic-type phosphine-borane interactions,

which was only the second dialkylplumbylene to ever have been structurally characterised. Using the

same methodology that was used for the Sn compound, extensive reduction of Pb occurred to

elemental lead. By using 1 equivalent of the dilithium salt [{nPr2P(BH3)}(Me3Si)CCH2][Li(THF)2]2 with

Cp2Pb, 17 formed in excellent yields after a simple work-up. Both rac- and meso- diastereoisomers

could be crystallised as discrete dialkylplumbylenes. The solid state structures confirm that there are

two B-H…Pb contacts for the rac-isomer with the meso-isomer having one contact slightly stronger.

As Pb is a larger atom, it enables a second, weaker Pb…H interaction in the meso-isomer that is not

observed for the Sn(II) analogue.

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Figure 9. rac-[{Me2P(BH3)}(Me3Si)C{(SiMe2)(CH2)}]2E, where E = Sn, 18, Pb, 19.

Two novel compounds were synthesised, a dialkylstannylene and a dialkylplumbylene, rac-

[{Me2P(BH3)}(Me3Si)C{(SiMe2)(CH2)}]2E where E = Sn, 18, Pb, 19, by Izod et al.12 in 2009 (Figure 9). In

both cases a dominance of the rac-isomer was observed, a consequence of the increased

stabilisation associated with two agostic-type interactions compared to the meso-isomer which only

has one. Both compounds 18 and 19 crystallise as discrete molecular species from Et2O with Sn or Pb

coordinated to the two carbanion centres of the ligand, generating a puckered seven-membered

ring. From DFT calculations, the HOMO in each case is the lone pair on E of essentially s character

whereas the LUMO in each case is the essentially pure, vacant pπ-orbital on E, therefore, there is

significant delocalisation of B-H σ-bonding electron density into the vacant pπ-orbital. As Pb has a

larger, more diffuse 6pπ-orbital than Sn’s 5pπ-orbital, Pb has a poorer overlap, thereby a decreased

energy interaction.

Figure 10. rac-[(RMe2Si){Me2P(BH3)}CH]2E, where E = Sn, Pb, R = Me, Ph, 20-23.

Acyclic dialkyltetrylenes have been prepared that are direct isoelectronic analogues of 11, which

favoured dimerisation, that was first reported by Lappert et al. in the 1970’s. The cyclic

dialkyltetrylenes, 18-19, are stabilised in the monomeric state12, by a combination of agostic-type

interactions and because of the steric bulk of the ligands used. The acyclic phosphine-borane

analogues, 20-21, were isolated in the monomeric form (Figure 10), providing evidence that agostic-

type interactions are sufficiently stabilising, without the need for steric bulk.

[(RMe2Si){Me2P(BH3)}CH]Li lithium salts were prepared in situ by the reaction between

Me2P(BH3)CH2Li and RMe2SiCl, followed by treatment with n-BuLi in THF, where R = Me, Ph. By

adding 0.5 equivalents of Cp2E in toluene, rac-[(Me3Si){Me2P(BH3)}CH]2E, where E = Sn, 20, Pb, 21,

respectively, were obtained as single crystal structures. rac-[(PhMe2Si){Me2P(BH3)}CH]2E, where E =

Sn, 22, Pb, 23, respectively, were also obtained (Figure 10).13 The meso-diastereomer was not

isolated which can be attributed to the stabilisation afforded by rac-20-23 having two agostic-type B-

12

H…E interactions instead of only one. 20-23 are all unambiguously monomeric in structure, showing

that the two agostic-type B-H…E interactions are sufficiently stabilising to disfavour dimerisation

which was also supported by DFT calculations. For the dimerisation of 20, the energy calculated was

+30.5 kcal mol-1 which clearly suggests that the energy gained on the formation of the Sn=Sn double

bond is insufficient versus the loss of the two B-H…Sn agostic-type interactions. These interactions

therefore provide a substantial barrier toward dimerisation.

Aims

To investigate phosphido-borane ligands, [R2P(BH3)]-, in the stabilisation of low oxidation states of

heavy group 14 metal centres by agostic-type interactions. To provide evidence that agostic-type

interactions between B-H…E can support the monomeric +II oxidation state of germanium, tin and

lead metal centres by disfavouring dimerisation. The research will be carried out in relation to

gaining knowledge and further insight into the fundamental science being observed regarding the

agostic-type interactions in these novel bis-phosphido-borane stabilised group 14 metal tetrylene

compounds. If +II metal centres can be stabilised through agostic-type interactions, the next

question is how this unique feature can be exploited, for example, in catalysis.

Approach

The precursor phosphines, R2PH, where R = Mes, Dipp, Ph, will be synthesised according to Schemes

2 and 3.

The synthesis of Mes2PH, 24, involves the metathesis reaction of two equivalents of the Grignard

reagent MesMgBr, and one equivalent of PCl3, to produce Mes2PCl, followed by hydride transfer

with LiAlH4 (Scheme 2).

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Scheme 2. Proposed synthesis of 24.

The synthesis of Ph2PH, 25, involves the reduction of Ph3P by sodium, followed by quenching with

NH4Br (Scheme 3).

Scheme 3. Proposed synthesis of 25.

Boronation of the phosphine with BH3.SMe2, followed by metalation of the product, R2P(BH3)H, with

n-BuLi, gives the phosphido-borane ligand, [R2P(BH3)]Li (Scheme 4).

Scheme 4. Proposed synthesis of [R2P(BH3)]Li.

The synthesis of novel phosphido-borane stabilised tetrylenes, [R2P(BH3)]2E, where E = Ge, Sn, Pb,

involves the metathesis reaction between two equivalents of the phosphido-borane ligands and ECl 2

(Equation 2). The compounds [R2P(BH3)]2E, will be isolated and characterised by XRD and NMR

spectroscopy.

Equation 2. Proposed synthesis of [R2P(BH3)]2E.

Results & Discussion

Synthesis and Characterisation of [Mes2P(BH3)]Li(THF)2 (26)

The research began with the methodology already in use by Izod et al. to afford dialkylphosphido-

borane lithium salts, [R2P(BH3)]Li, where R = Mes, 26, Dipp, 27, Ph, 28. Compounds 26-28 could then

be used as metathesis reagents for reaction with tin dichloride, SnCl2, with the aim to isolate and

characterise bis-(dialkylphosphido-borane) stannylenes, [R2P(BH3)]2Sn.

14

Dimesitylphosphine, Mes2PH, 24, was synthesised, as shown in Scheme 5, as the precursor to the

dimesitylphosphido-borane lithium salt, [Mes2P(BH3)]Li(THF)2, 26.

Scheme 5. Synthesis of 24.

The reaction of one equivalent of 24 with one equivalent of BH3.SMe2 solution in THF, afforded

complete conversion to dimesitylphosphine borane, Mes2P(BH3)H, 29, after one hour at room

temperature. The 31P NMR spectrum of the isolated crystalline product is shown in Figure 11, which

contains a broad doublet at -28.3 ppm (JPH = 387.6 Hz).

Figure 11. 31P NMR spectrum of 29 in CDCl3.

One equivalent of n-butyllithium solution in n-hexane was added to afford complete conversion of

29 to 26, shown in the 31P NMR spectrum of the isolated product (Figure 12) which contains a single,

broad doublet at -55.9 ppm (JPH = 47.2 Hz). The 11B{1H} NMR spectrum contains a broad doublet at -

31.9 ppm (JPB = 36.7 Hz) (Figure S8).

15

-95-90-85-80-75-70-65-60-55-50-45-40-35-30-25-20-15-10-50f1 (ppm)

-65-60-55-50-45-40-35-30-25-20-15-10-505f1 (ppm)

Figure 12. 31P NMR spectrum of 26 in THF-d8/toluene-d8.

The volatile THF was evaporated in vacuo, before diethyl ether was added, where upon pale yellow

crystals of 26 precipitated out of solution at room temperature. XRD confirmed the structure as that

of 26, shown in Figure 13.

Figure 13. X-ray crystal structure of 26 with

carbon bound hydrogen atoms omitted for

clarity. Selected bond lengths (Å) and angles (°):

P-B 1.967(2), B…Li 2.426(3), P-Li(1A) 2.645(3), P-

C(1) 1.8505(16), P-C(10) 1.8504(16), P-B…Li

139.76(12).

Compound 26 crystallises as a cyclical dimeric structure, wherein each phosphorus atom is bound to

a borane group and a lithium cation. Two of the borane hydrogen atoms have contacts with a

lithium ion, in an agostic-type interaction, stabilising the compound. Two molecules of the donor

tetrahydrofuran solvent are coordinated to each lithium atom.

The bond lengths of P-C(1) and P-C(10) are 1.8505(16) Å. The P-B bond length is 1.967(2) Å, similar to

a phosphido-borane lithium salt, [{Ph2P(BH3)}CHPiPr2]Li(tmeda), 30, characterised by Izod et al.13,

which has a slightly smaller P-B length of 1.933(2) Å (Figure 14). The B…Li distances in 26 are 2.426(3)

Å, the same length as the B…Li distances in 30 of 2.442(4) Å.24

Figure 14. X-ray crystal structure of 30 with carbon

bound hydrogen atoms omitted for clarity. Selected

bond lengths (Å): P-B 1.933(2), B…Li 2.442(4).

16

-95-90-85-80-75-70-65-60-55-50-45-40-35-30-25-20-15-10f1 (ppm)

Mes2PLi(THF)2

BH3

Mes2P Li(THF)2BH3

BH3Mes2PH

The P-Li1 contacts within 26 are 2.645(3) Å. Compared to the P-Li distances of

2.479(11) Å and 2.483(1) Å in the phosphide lithium salt dimer,

[(Mes2P)Li(OEt2)]2, 31, crystallised by Power et al.25 (Figure 15), this is a longer

distance than expected. Figure 15. Structure of 31.

Hydrolysis of 26 to [Mes2P(BH3)2]Li(THF)2 (32) and 24

It was found that 26 can decompose through a hydrolysis pathway to dimesitylphosphido-bis-

(borane) lithium salt, [Mes2P(BH3)2]Li(THF)2, 32, and the starting phosphine 24. The proposed

mechanism is the nucleophilic attack of 26 on the borane of a molecule of 29, to afford 32 and 24

(Scheme 6). This can be attributed to the increased nucleophilicity of 32 with respect to 29.

Scheme 6. The hydrolysis mechanism of 26 to 32 and 24.

Integration of the peaks in the 31P NMR spectrum gave the ratio of the products, 26:32:24, as 8:1:1

(Figure 16). As the ratio of 32 and 24 are equal, this suggests the proposed hydrolysis pathway is

correct. The sample was re-analysed by 31P NMR spectroscopy after three days, with an increase in

the hydrolysis products observed, at a ratio of 26:32:24 of 5:1:1.

17

Figure 16. 31P NMR spectrum of 26 and the corresponding hydrolysis products 32 and 24 in THF-d8/toluene-d8.

A broad unresolved septet, due to the coupling of phosphorus to two 11B quadrupolar active nuclei (I

= 3/2), can be seen at -10.8 ppm in the 31P NMR spectrum, and also a sharp doublet at -93.4 ppm (JPH

= 228.3 Hz), which correspond to 32 and 24 respectively.

Synthesis and Characterisation of 32

Compound 32 was isolated to confirm the identity of the decomposition product by comparison of

the signals observed in the 31P NMR spectra. Two equivalents of BH3.SMe2 in n-hexane solution was

added to one equivalent of 29 in THF, to yield 32, shown in the 31P{1H} NMR spectrum of the product

(Figure 17), which contains a broad singlet at -21.2 ppm. The change of solvent from THF-d8/toluene-

d8 to CDCl3 has a pronounced effect on the chemical shift but the multiplet observed unequivocally

corresponds to that of 32.

Figure 17. 31P{1H} NMR spectrum of 32 in CDCl3.

18

-60-55-50-45-40-35-30-25-20-15-10-505101520f1 (ppm)

The THF was removed in vacuo, before diethyl ether was added, whereupon pale yellow crystals of

32 precipitated out of solution. XRD confirmed the structure as that of 32 (Figure 18).

Figure 18. X-ray crystal structure of 32

with carbon bound hydrogen atoms

omitted for clarity. Selected bond lengths

(Å) and angles (°): P-B(1) 1.9655(19), P-

B(2) 1.9619(18), B(1)…Li 2.455(4), B(2)…Li

2.505(4), P-C(1) 1.8419(16), P-C(10)

1.8464(16), P-B(1)…Li 89.70(11), P-B(2)…Li

88.33(10).

Compound 32 crystallises as a monomer with two coordinated disordered THF solvent molecules.

The phosphorus atom is bound to two mesityl groups and to two borane groups. The borane groups

are coordinated to lithium through B-H…Li contacts with different hapticities. Interestingly, two B-H…

Li contacts are observed for one borane group whereas the second borane group only has one B-H …

Li contact.

The P-C(1) and P-C(10) bond lengths are 1.8419(16) Å and 1.8464(16) Å respectively, equal in length

to that of the P-C(1) and P-C(10) bond lengths in 26, of 1.8505(16) Å. The P-B(1) and P-B(2) bonds are

of essentially identical lengths of 1.9655(19) Å and 1.9619(18) Å respectively. The P-B bond lengths

are similar to that of 26.

The B(1)…Li distance, with two B-H…Li contacts, has a length of 2.455(4) Å compared to the distance

of B(2)…Li, with only one B-H…Li contact of 2.505(4) Å. The B(1)-H…Li contact can be said to be slightly

stronger because of the increased hapticity versus that of the B(2)-H…Li contact. Compound 26, with

two B-H…Li contacts, has a smaller B...Li distance of 2.426(3) Å, implying the interactions in 26 are

slightly stronger still, as there is only one borane group in the molecule able to add stability through

agostic-type interactions.

Attempted Synthesis of [Mes2P(BH3)]2Sn (33)

19

Mes2P Li(THF)2BH3

BH3Mes2PH

BH3 Mes2PH

In an attempt to synthesise bis-(dimesitylphosphido-borane) stannylene, [Mes2P(BH3)]2Sn, 33

purified and isolated crystals of 26 were used as metathesis reagents for reaction with SnCl2.

A solution of two equivalents of 26 in THF was added dropwise to SnCl2 at -78 °C in THF, and the

resulting solution was slowly warmed to room temperature. After three hours, elemental tin

particulates were observed in the reaction mixture. The observed species in the 31P NMR spectrum

suggest that the reaction material contained none of the desired compound and had completely

decomposed. A mechanism of radical-based reductive elimination followed by a hydrogen radical

being removed from the solvent was postulated for the decomposition of 33 to elemental tin and

the corresponding products observed below in Figure 19.

Figure 19. 31P NMR spectrum of the reaction between two equivalents of 26 and SnCl2 in THF.

The characteristic broad signals for tin-containing phosphido-borane compounds with 119Sn satellite

peaks are absent from the 31P NMR spectrum. The hydrolysis products of 26 are once again

observed, in the ratio of 26:32:24 of 1:1:1.

The rapid decomposition can be attributed to three factors: (i) The P-Sn bond is weaker and more

easily reduced than a C-Sn bond (ii) The lack of a lone pair on phosphorus means it cannot stabilise

the electron deficient Sn(II) centre by pπ-pπ interactions26 (iii) Mesityl aromatic rings, with three

methyl substituents, causes the rings to be very electron rich. Electron density is pushed to

phosphorus, increasing the nucleophilicity of the ligand. This effect increases the likelihood of

reduction of the Sn(II) centre to Sn(0).

Synthesis of [Dipp2P(BH3)]Li (27)20

-95-90-85-80-75-70-65-60-55-50-45-40-35-30-25-20-15-10-5f1 (ppm)

Dipp R groups are sterically bulkier than mesityl R groups, decreasing the tendency of the

phosphido-borane ligands to dimerise. The fact that there are only two alkyl chains on the dipp

aromatic ring compared to three methyl groups on the mesityl aromatic ring also means the ring is

relatively less electron rich. Less electron density can therefore be centred on the phosphorus atom.

The effect is a less nucleophilic phosphorus atom, which corresponds to a

decreasing likelihood of the stannylene, [Dipp2P(BH3)]2Sn, 34, being reduced from

the stabilised +2 oxidation state to elemental tin with the production of

diphosphine borane, Dipp2P(BH3)-P(BH3)Dipp2. Compound 27 was synthesised for

metalation with SnCl2, to investigate the stabilisation effect of these ligands on

the low valent Sn(II)centre.

Figure 20. Structure of Dipp2PH, 35.

One equivalent of BH3.SMe2 solution was added to one equivalent of 35 in diethyl ether to synthesise

the phosphine borane, Dipp2P(BH3)H, 36. Subsequently, one equivalent of n-butyllithium was then

added to the resulting solution to form 27 in situ. This is shown in the 31P{1H} NMR spectrum of the

product which contains a broad, quartet at -73.5 ppm (JPB = 36.4 Hz) (Figure 21).

Figure 21. 31P{1H} NMR spectrum of in situ generated 27 in diethyl ether.

21

-105-100-95-90-85-80-75-70-65-60-55-50-45-40-35-30-25-20f1 (ppm)

Dipp2P LiBH3

BH3

Dipp2P(BH3)H

Dipp2PH

An excess of the borane solution was added accidently, which accounts for the larger than expected

broad, unresolved septet signal at -24.1 ppm which corresponds to the bis-phosphido-borane

lithium salt, [Dipp2P(BH3)2]Li, 37. A small sharp singlet at -102.1 ppm corresponding to 35 is also

noted.

Attempted Synthesis of 34

The reaction mixture described above was added dropwise to tin dichloride, at -78 °C, and slowly

warmed to room temperature (Figure 22). The resulting orange-yellow solution decomposed in

under an hour to produce a black solution and large amounts of fine elemental tin particulates. This

can be attributed to the rapid reduction of 34 to elemental tin. The fact that the expected reduction

product, Dipp2(BH3)P-P(BH3)Dipp2, is not observed, leads to the conclusion that the compound is

highly unstable, due to the large steric hindrance within the molecule. This causes the further

decomposition to the less hindered Dipp2P-PDipp2, and free borane in solution, the former

corresponding to the insignificant singlet at -37.6 ppm.

The 31P{1H} NMR spectrum shows no evidence of any tin-containing phosphido-borane compounds.

Compound 36 can be seen as a broad, unresolved quartet at -32.2 ppm. The hydrolysis products of

37 and 35, due to the broad, unresolved septet at -24.1 ppm and the sharp singlet at -102.9 ppm,

respectively, provide further evidence for this decomposition pathway.

Figure 22. 31P{1H} NMR spectrum of the reaction of 27 with SnCl2 after one hour in diethyl ether.

22

-105-100-95-90-85-80-75-70-65-60-55-50-45-40-35-30-25-20f1 (ppm)

Synthesis of [Ph2P(BH3)]Li (28)

To investigate more fully the hypothesis that the large steric bulk of the mesityl and dipp R groups

were the major cause of the rapid decomposition of bis-(dialkylphosphido-borane) stannylenes, the

smaller diphenylphosphido-borane lithium salt, [Ph2P(BH3)]Li, 28, was synthesised in situ for the

metathesis reaction with SnCl2.

Compound 25 was synthesised as the precursor to 28 (Scheme 7).

Scheme 7. Synthesis of 25.

The reaction of one equivalent of 25 with one equivalent of BH3.SMe2 solution in THF afforded

diphenylphosphine borane, Ph2P(BH3)H, 38, after one hour at room temperature (Figure 23).

Figure 23. 31P NMR spectrum of 38 in CDCl3.

The 31P NMR spectrum of the product contains a broad doublet at 1.9 ppm (JPH = 389.17 Hz).

To the resulting solution, one equivalent of n-butyllithium solution was added and this mixture was

stirred for 1 h to afford a red solution of 28 in situ. This is shown in the 31P NMR spectrum of the

product, which contains a single, broad quartet at -32.6 ppm (JPB = 21.5 Hz) (Figure 24).

23

-80-75-70-65-60-55-50-45-40-35-30-25-20-15-10f1 (ppm)

-70-60-50-40-30-20-1001020304050607080f1 (ppm)

Figure 24. 31P NMR spectrum of in situ generated 28 in THF.

Attempts to crystallise 28 were unsuccessful due to the oil-like nature of the product in THF, toluene,

methylcyclohexane and dimethoxyethane solvents.

Synthesis of [Ph2P(BH3)2]Li (39)

One equivalent of n-butyllithium solution was added to one equivalent of 25 in THF to afford a red

solution of [Ph2P]Li in situ. Subsequent addition of two equivalents of BH3.SMe2 solution afforded the

diphenylphosphido-bis-(borane) lithium salt, [Ph2P(BH3)2]Li, 39, in situ (Figure 25).

Figure 25. 31P{1H} NMR spectrum of in situ generated 39 in THF.

The 31P{1H} NMR spectrum of the product contains a single, broad multiplet at -7.2 ppm. Attempts to

crystallise 39 were unsuccessful due to the oil-like nature of the product in a number of solvents.

Attempted Synthesis of [Ph2P(BH3)]2Sn (40)

In an attempt to synthesise bis-(diphenylphosphido-borane) stannylene, [Ph2P(BH3)]2Sn, 40, the

reaction solution of 39 described above was used in the metathesis reaction with SnCl2.

Two equivalents of 39 were added dropwise to one equivalent of SnCl2 in THF, at -78 °C, and this

mixture was slowly warmed to room temperature.

24

-50-40-30-20-10-5051015202530354045505560f1 (ppm)

The 31P{1H} NMR spectrum of the reaction mixture (Figure 26), shows two tin-containing products of

the metathesis reaction; a broad singlet at -10.1 ppm with 119Sn satellite peaks (JSnP = 1632 Hz) and an

unidentified broad singlet at -6.7 ppm with 119Sn satellite peaks (JSnP = 1690 Hz). Later experiments

concluded that the signal at -10.1 ppm corresponds to the unexpected product tris-

(diphenylphosphido-borane) stannate, [(Ph2P(BH3))3Sn]Li(THF), 41.

Figure 26. 31P{1H} NMR spectrum of two Sn compounds one hour after the reaction of in situ generated 39 and SnCl2 in THF.

The volatiles were removed in vacuo. Toluene was added and the solution was filtered through

celite. Consequently, only 41 was observed in the 31P NMR spectrum (Figure 27). The unidentified

product therefore was stable in THF solvent but not in toluene.

25

-55-45-35-25-15-505101520253035404550f1 (ppm)

JSnP = 1632 Hz

Figure 27. 31P{1H} NMR spectrum of 41 in THF-d8/toluene-d8.

The 31P{1H} NMR spectrum of the reaction mixture contains a broad singlet at -16.6 ppm,

corresponding to 41 with broad 119Sn satellite peaks (JSnP = 1632 Hz). Other minor products observed

in the reaction mixture are that of 38, the broad multiplet at -0.6 ppm, and 28, the broad multiplet

at -10.8 ppm.

Direct Synthesis and Characterisation of 41

A directed synthesis of this compound was undertaken to get a clean sample of 41 to confidently

assign the peaks observed in the NMR spectra. To isolate 41, three equivalents of 28 were added

dropwise to one equivalent of SnCl2 in THF, at -78 °C, and this mixture was warmed slowly to room

temperature. The volatile THF was removed in vacuo. Toluene was added to the resulting solid and

the pale solids were removed by filtration. Crystals suitable for X-ray crystallography were obtained

from a concentrated solution of 41 in toluene, stored at -25 °C.

The 31P NMR spectrum of the isolated crystals contains a broad singlet at -12.4 ppm (JSnP = 1632 Hz),

due to 41, along with a small unidentified broad multiplet at -18.7 ppm (Figure 28).

26

JSnP = 1632 Hz

-95-90-85-80-75-70-65-60-55-50-45-40-35-30-25-20-15-10-505f1 (ppm)

Figure 28. 31P NMR

spectrum of 41 in THF-

d8/toluene-d8.

The 119Sn NMR spectrum (Figure 29) contains a single sharp quartet at 59 ppm (JSnP = 1632 Hz)

confirming that the product is 41.

Figure 29. 119Sn NMR spectrum of 41 in THF-d8/Toluene-d8.

Compound 41 crystallises as a monomer with one disordered THF solvent molecule (Figure 30). The

centre tin atom is bound to three phosphorus atoms. The borane groups all have agostic-type

interactions with the lithium cation. Interestingly, two of the borane hydrogens of two BH 3 groups

have contacts with lithium but in the third borane group, there is only one B-H …Li contact. The P-Sn

bonds are of differing lengths; Sn-P2 is the longest bond at 2.6444(13) Å compared to Sn-P1 and Sn-

P3 lengths of 2.6097(14) Å and 2.6288(13) Å, respectively. The bonds between P-B are all of

statistically equal lengths with an average of 1.954(6) Å, equal to the lengths shown previously in 26

and 32.

27

-21-20-19-18-17-16-15-14-13-12-11-10-9-8-7-6-5-4f1 (ppm)

-85-80-75-70-65-60-55-50-45-40-35f1 (ppm)

JSnP = 1632 Hz

Figure 30. X-ray crystal structure of 41 with

carbon bound hydrogen atoms omitted for

clarity. Selected bond lengths (Å) and angles

(°) shown in Table 1.

The length of the B2…Li distance is rather long at 2.798(14) Å, compared to the lengths of the B(1)…Li

and B(3)…Li distances at 2.470(13) Å and 2.477(14) Å, respectively. This is explained by the reduced

hapticity of the B(2)-H…Li contact versus the hapticity observed in both the B(1)-H…Li and B(3)-H…Li

contacts. The B(1)-H…Li and B(3)-H…Li contact lengths are similar to 26 and 32.

Izod et al.27 synthesised the only other known compound of this nature, tris-(diisopropylphosphido-

borane) stannate, [({(CH3)2CH}2P(BH3))3Sn]Li(THF)3, 42 (Figure 31) Whereas in 41, all three borane

groups are coordinated to lithium, in 42 only one of the borane groups is, with the other two

remaining uncoordinated. The bond lengths of Sn to P(1), P(2), and P(3) are 2.6349(6) Å, 2.6219(6) Å

and 2.6241(6) Å, respectively. All P-B bond lengths are equal at 1.957(3) Å. The length of the B(1) …Li

distance in 42 is smaller than the B…Li

distances in 41 at 2.381(5) Å, because the

agostic-type interactions are spread over

only one BH3 group with two B-H…Li

contacts in 42, whereas in 41, the

interactions are spread over three BH3

groups with five B-H…Li contacts.

28

Figure 31. X-ray crystal structure of 42 with carbon bound hydrogen atoms omitted for clarity. Selected bong lengths (Å)

and angles (°) shown in Table 1.

The bond angle of P(1)-B(1)…Li is extremely large at 148.32(18)° compared to 41’s P(1, 2, 3)-B(1, 2, 3)…Li bond angles of 114.8(4)°, 97.0(3)° and 108.4(4)°, respectively. This is attributed to the constraint

of all three BH3 groups coordinated through B-H…Li contacts in 41.

In 2010, Izod et al.28 synthesised [[{(Me3Si)2CH}

(Ph)P]3Sn]Li(THF)4, 43, with Sn-P bond lengths of 2.649(2) Å and P-

Sn-P bond angles of 91.41(6)° (Figure 32). These are

significantly smaller than the bond angles of 41 at 93.60(4)°,

95.17(5)° and 95.56(5)°. This is explained by the requirement of

the bond angles in 41 to widen to incorporate the BH3 groups.

Figure 32. Structure of 43.

Bond Length (Å)/ Bond Angle (°)

[(Ph2P(BH3))3Sn]-Li(THF), 41

[({(CH3)2P(BH3))3Sn]-Li(THF)3, 42

[[{(Me3Si)2CH}(Ph)P]3Sn]-Li(THF)4, 43

Sn-P 2.6097(14)

2.6444(13)

2.6288(13)

2.6349(6)

2.6219(6)

2.6241(6)

2.649(2)

B-Li 2.470(13)

2.798(14)

2.477(14)

2.381(5) n/a

P-B-Li 114.8(4)

97.0(3)

108.4(4)

148.32(18) n/a

P-Sn-P 95.17(5)

93.60(4)

95.56(5)

103.459(19)

104.400(19)

103.853(18)

91.41(6)

Table 1. Selected bond lengths (Å) and angles (°) of 41, 42, and 43.

Decomposition of 41

29

Ph2P Li(THF)2BH3

BH3

Ph2PH

Ph2PHBH3

[{Ph2P(BH3)}2Sn(X)]

Analysis by 31P{1H} and 119Sn{1H} NMR spectroscopy of the sample shown in Figure 27, conducted

after two days in THF-d8/toluene-d8 solvent, shows the partial decomposition of 41 (Figures 33 and

34). Notable identified peaks in the 31P{1H} NMR spectrum are for 41 at -15.4 ppm and the hydrolysis

products 39, at -10.1 ppm and 25, at -41.2* ppm. A large broad multiplet is observed at 1.9 ppm

which corresponds to 38, a consequence of 41 being highly unstable in solution. One of the major

products observed is not for 41, but instead for an unidentified tin-containing compound, due to the

broad multiplet at 70.6 ppm. The 119Sn satellites were not fully resolved but the broad multiplet

signal is characteristic of tin- compounds.

Figure 33. 31P{1H}

NMR

spectrum of the partial decomposition of 41 in THF-d8/toluene-d8.

Figure 34. 119Sn{1H} NMR spectrum of the partial decomposition of 41 in THF-d8/toluene-d8.

30

-45-35-25-15-50515253545556575f1 (ppm)

-280-240-200-160-120-80-4004080120160200f1 (ppm)

The 119Sn{1H} NMR spectrum of the solution contains a sharp quartet at -75 ppm due to 41. A second,

sharp triplet signal at -32 ppm is also observed, due to a compound of the general formula

[{Ph2P(BH3)}2Sn(X)]-. It is reasonable to conclude that the signal observed in the 31P{1H} NMR

spectrum at 70.6 ppm and the signal observed in the 119Sn{1H} NMR spectrum at -32 ppm are for the

same compound, [{Ph2P(BH3)}2Sn(X)]-. The broad nature of the 31P signal and the triplet multiplicity of

the 119Sn signal provide the evidence for this statement.

After five days in a sealed NMR tube in THF-d8/toluene-d8 solvent, the complete decomposition of 41

was observed (Figure 35).

Figure 35. 31P{1H} NMR spectrum of the complete decomposition of 41 after five days in THF-d8/toluene-d8.

Elemental tin particulates were observed throughout the now colourless solution, along with the

insignificant sharp singlet at 20.1 ppm due to Ph2P-PPh2, providing evidence that reduction had

occurred. The major product is 38, the broad multiplet seen at 0.71 ppm, along with a substantial

amount of the unidentified [{Ph2P(BH3)}2Sn(X)]- compound, corresponding to the broad multiplet at

70.5 ppm. This product was never isolated, but it can be concluded that [{Ph 2P(BH3)}2Sn(X)]- is in fact

the thermodynamic stable product versus 41.

Aromatic R groups, being electron rich, when bound to phosphorus push electron density onto P.

Alkyl groups connected to the aromatic ring further increase the electron density in the ring, in turn,

increasing the electron density centralised on phosphorus. The more electron rich P is, the increased

likelihood of decomposition of [R2P(BH3)]2Sn. This investigation has shown that compounds

containing dipp groups (two alkyl chains) are the most prone to decomposition, followed by mesityl

groups (three methyl groups), with phenyl groups being the most stable.

Two diphenylphosphido-borane ligands are too small to prevent attack of a third ligand. The

electron-poor Sn(II) centre readily accepts a further phosphido-borane ligand to become electron-

31

-35-25-15-505101520253035404550556065707580f1 (ppm)

precise. Technically this is not a phosphido-borane stabilised stannylene as a stannylene is defined as

a stabilised low valent Sn centre. This leads to the conclusion that aromatic diphosphido-borane

substituted stannylenes are too unstable to be isolated.

Synthesis of [Mes2P(BH3)CHPh]Li (44)

The investigation into synthesising bis-dialkylphosphido-borane stannylenes was shown to be

unsuccessful. The class of compounds are highly thermally and photo chemically unstable, and prone

to decomposition through reduction and hydrolysis pathways. Dialkylphosphido-borane carbanion

ligands have been previously synthesised by Izod et al. and have been used to stabilise low valent

heavy group 14 metal centres (E = Sn, Pb) through agostic-type interactions.11-13 Compound 44 was

synthesised as a derivative of this class of carbanion ligands to be used in the metathesis reaction

with stannocene, SnCp2.

One equivalent of n-butyllithium was added to one equivalent of Mes2P(BH3)CH2Ph, 45, in THF to

afford 44 in situ. This is shown in the 31P NMR spectrum of the product (Figure 36) which contains a

broad multiplet at -0.6 ppm, the major product 44.

Figure 36. 31P NMR spectrum of in situ generated 44 in THF.

The volatile THF was removed in vacuo before toluene was added to the resulting pale solid. Two

equivalents of 44 in situ were added to SnCp2 in toluene at room temperature to afford an orange-

yellow solution after one hour (Figure 37).

32

-45-40-35-30-25-20-15-10-5051015202530354045f1 (ppm)

Figure 37. 31P NMR spectrum of the reaction of 44 and SnCp2 in toluene.

The 31P NMR spectrum of the solution contains two broad signals at 14.4 ppm and 19.1 ppm,

potentially diastereoisomers of each other, as was observed for the compounds isolated by Izod et

al. previous.10-12 The broad shape of the signals are expected for tin-containing phosphido-borane

compounds. The 119Sn satellites are not resolved because of the poor signal to noise ratio. Current

work by Izod et al. is on-going to isolate and characterise the products contained in the reaction

mixture.

There are a small number of dialkyltetrylenes that have been synthesised and characterised by Izod

et al. over recent years (Figures 8-10). The electron-deficient Sn(II) centres are stabilised through

agostic-type interactions with the BH3 substituents. As the phosphine-borane group is an extra atom

further from the Sn(II) centre, the interaction between B-H…Sn is in a more favourable orientation

than for phosphido-borane ligands, where the phosphorus atom is adjacent to the Sn(II) centre. The

tight angle in the latter forces the agostic-type interactions into unfavourable orientations and

therefore cannot efficiently stabilise the Sn(II) centre. From the crystal structure data analysed of 41,

no agostic-type B-H…Sn contacts were observed leading to the conclusion that the bite angle is too

small for effective stabilisation.

Conclusion

Compounds 26 and 32 were synthesised and isolated. The molecular structures of 26 and 32 contain

agostic-type interactions between the borane moieties and the lithium cation, providing effective

33

-45-35-25-15-50510152025303540455055f1 (ppm)

stabilisation of these compounds. Somewhat unexpectedly, different hapticities of these interactions

are observed.

The investigation into the synthesis and consequent isolation of phosphido-borane stabilised

stannylenes, [R2P(BH3)]2Sn, where R = Mes, Dipp, Ph, was unsuccessful, due to the rapid

decomposition of the products to elemental tin, among other ligand side products.

The weaker P-Sn bonds are a major factor in their instability versus the C-Sn bonds in phosphine-

borane substituted alkyl stannylenes, [R2P(BH3)CR’2]2Sn, because the P-Sn bond has an increased

tendency to be reduced. In part, the decomposition of 40 can be attributed to the fact the

phosphorus lone pair is bound to the borane moiety and therefore there is no pπ-pπ overlap

between phosphorus and the low valent Sn(II) centre.

Phosphine-borane stabilised alkyl ligands have been shown to have a favourable orientation of the

borane moieties with the electron-poor tin centre that allows for efficient overlap of B-H σ-orbitals

with the pπ-orbital of Sn. The agostic-type interactions stabilise the low valent Sn(II) centre through

donation of electron density into the tin pπ-orbital. This interaction cannot occur in phosphido-

borane substituted stannylenes as phosphorus is adjacent to the tin centre causing the unfavourable

orientation of the tin centre with the borane moieties due to the constrained angle. The low valent

tin centre therefore is not stabilised by agostic-type interactions in phosphido-borane substituted

stannylenes.

Compound 41 was isolated due to the smaller nature of phenyl groups compared to mesityl and dipp

groups. The X-ray crystal structure of 41 contains no agostic-type interactions between B-H σ-

orbitals and Sn pπ-orbitals. The electron-precise tin centre is instead stabilised through a

combination of the favourable steric and electronic effects of the ligands.

The investigation into bis-(phosphido-borane) stannylenes and the consequent absence of evidence

of their synthesis by 11B, 31P and 119Sn NMR spectroscopy demonstrates the highly unstable nature of

this class of compounds. Future work will therefore not focus on the isolation of phosphido-borane

substituted tetrylenes. Instead, the synthesis and isolation of further sterically demanding

phosphine-borane substituted alkyl tetrylenes, [R2P(BH3)CR’2]2E, will be explored. Characterisation by

XRD will provide further evidence for the stabilisation of low valent group 14 tetrylene centres due

to agostic-type interactions.

34

Experimental

All manipulations were carried out using standard Schlenk techniques under an atmosphere of dry

argon. Diethyl ether, THF and light petroleum (b.p. 40-60 °C) were dried prior to use by distillation

under nitrogen from sodium or sodium/potassium alloy and were stored over a potassium film.

Deuterated toluene was distilled from potassium and stored over activated 4Å molecular sieves.

Borane dimethyl sulphide and n-butyllithium were prepared as stock solutions in n-hexane or

toluene and were dried prior to use over activated 4Å molecular sieves. All other compounds were

used as supplied by the manufacturer.

1H, 11B and 31P NMR spectra were recorded on a Bruker Avance III 300 spectrometer operating at

300, 96.25 and 121.44 MHz, respectively, a Bruker Avance II 400 spectrometer operating at 400,

128.34 and 161.92 MHz, respectively, or a Bruker Avance III 500 spectrometer operating at 500,

160.42 and 202.40 MHz, respectively; chemical shifts are quoted in ppm relative to

tetramethylsilane, external BF3.Et2O and 85% H3PO4. 7Li, 13C{1H} and 119Sn{1H} NMR spectra were

recorded on a Bruker Avance III 500 spectrometer operating at 194.32, 125.73 and 186.45 Hz,

respectively; chemical shifts are quoted in ppm relative to 9.7 M LiCl, tetramethylsilane and Me 4Sn,

respectively.

Mes2PH (24)

To a solution of PCl3 (3.43 g, 25 mmol) in diethyl ether (50 mL) was added a solution of MesMgBr (50

mL, 1.0 M, 50 mmol) in diethyl ether (50 mL) at -78 °C. The resulting yellow solution was warmed

slowly to room temperature and filtered. The filtrate was cooled (0 °C) before LiAlH4 (0.95 g, 25

mmol) was added in portions. The mixture was stirred for 30 min and slowly warmed to room

temperature. The reaction was quenched with degassed H2O (50 mL). The organic layer was

decanted and further extracted with cold petrol (3 x 30 mL). The combined organic layers were dried

over molecular sieves. The volatiles were removed in vacuo to give a yellow solid, which was heated

at 70 °C in vacuo to yield 24 as a pale yellow crystalline solid. Yield 5.78 g, 85.6%. 1H NMR (CDCl3, 25

°C): δ 2.22 (s, 6H, p-CH3), 2.24 (s, 12H, o-CH3), 5.23 (d, JPC = 232.90 Hz, 1H, PH), 6.80 (m, 4H, ArH). 31P{1H} NMR (CDCl3, 25 °C): δ -93.1 (s).

Mes2P(BH3)H (29)

35

To a solution of Mes2PH (0.08 g, 0.30 mmol) in THF (10 mL) was added a solution of BH3.SMe2 in THF

(0.18 mL, 1.68 M, 0.30 mmol) and the solution was stirred for 1 h. The volatiles were removed in

vacuo to give 29 as a pale yellow solid, which was sufficiently clean for use without further

purification. Yield 0.07 g, 83.3%. 1H{11B} NMR (CDCl3, 25 °C): δ 1.23, (dd, JPH = 14.55 Hz, JHH = 7.25 Hz,

3H, BH3), 2.25 (s, 6H, p-CH3), 2.36 (s, 12H, o-CH3), 6.60 (dq, JPH = 383.94 Hz, JHH = 7.63Hz, 1H, PH), 6.85

(m, 4H, m-ArH). 13C{1H} NMR (CDCl3, 25 °C): δ 21.16 (CH3), 21.99 (d, JPC = 6.16 Hz, CH3), 122.05 (d, JPC =

51.20 Hz, Ar), 130.37 (d, JPC = 8.22 Hz, Ar), 141.17 (Ar), 142.55 (d, JPC = 8.47 Hz, Ar). 11B{1H} NMR

(CDCl3, 25 °C): δ -34.7 (s, br). 31P{1H} NMR (CDCl3, 25 °C): δ -28.3 (m, br).

[Mes2P(BH3)]Li(THF)2 (26)

To a solution of Mes2P(BH3)H (0.71 g, 2.50 mmol) in THF (20 mL) was added a solution of n-BuLi in

hexanes (1.0 mL, 2.49 M, 2.50 mmol) and the resulting red solution was stirred for 1 h. The volatiles

were removed in vacuo. Diethyl ether (20 mL) was added to the resulting pale solid. The solution

was reduced to 10 mL and stored at -25 °C overnight. Crystals suitable for X-ray crystallography of 26

were obtained. Isolated yield: 0.50 g, 66.2%. 1H{11B} NMR (THF-d8/toluene-d8, 25 °C): δ 1.13 (d, JPH =

7.13 Hz, 3H, BH3), 1.76 (m, THF), 2.17 (s, 6H, p-CH3), 2.50 (s, 12H, o-CH3), 3.74 (m, THF), 6.68 (s, 4H,

m-ArH). 13C{1H} NMR (THF-d8/toluene-d8, 25 °C): δ 20.37 (CH3), 23.42 (d, JPC = 12.43 Hz, CH3), 25.33

(THF), 67.23 (THF), 128.17 (d, JPC = 2.24 Hz, Ar), 132.40 (Ar), 141.08 (d, JPC = 10.61 Hz, Ar), 143.23 (d,

JPC = 25.86 Hz, Ar). 7Li NMR (THF-d8/toluene-d8, 25 °C): δ -0.7 (s, br). 11B{1H} NMR (THF-d8/toluene-d8,

25 °C): δ -31.9 (d, JPB = 37 Hz). 31P{1H} NMR (THF-d8/toluene-d8, 25 °C): δ -55.9 (s, br).

[Mes2P(BH3)2]Li(THF)2 (32)

To a solution of Mes2P(BH3)H (0.21 g, 0.73 mmol) in THF (20 mL) was added a solution of n-BuLi in

hexanes (0.3 mL, 2.49 M, 0.75 mmol) and the solution was stirred for 1 h. A solution of BH 3.SMe2 in

THF (0.4 mL, 2M, 0.73 mmol) was added and the mixture was stirred for 1 h. The volatiles were

removed in vacuo. Diethyl ether (20 mL) was added to the resulting pale solid. The solution was

reduced to 10 mL and stored at -25 °C overnight. Crystals suitable for X-ray crystallography of 32

were obtained. Isolated yield: 0.37 g, 94.5%. 1H{11B} NMR (CDCl3, 25 °C): δ 1.06 (d, JPH = 7.6 Hz, 6H,

BH3), 1.76 (m, THF), 2.18 (s, 6H, p-CH3), 2.30 (s, 12H, o-CH3), 3.61 (m, THF), 6.70 (s, m-ArH). 13C{1H}

NMR (CDCl3, 25 °C): δ 20.79 (CH3), 23.19 (CH3), 25.87 (THF), 67.65 (THF), 129.91 (d, JPC = 7.59 Hz, Ar) ,

141.70 (d, JPC = 7.34 Hz, Ar). 7Li NMR (CDCl3, 25 °C): δ 0.0 (m, br). 11B{1H} NMR (CDCl3, 25 °C): δ -29.0

(m, br). 31P{1H} NMR (CDCl3, 25 °C): δ -21.2 (s, br).

36

Dipp2P(BH3)H (36)

To a solution of Dipp2PH (0.18 g, 0.51 mmol) in diethyl ether (20 mL) was added a solution of

BH3.SMe2 in THF (0.3 mL, 1.68 M, 0.51 mmol) and the solution was stirred for 1 h. The volatiles were

removed in vacuo to give 36 as a pale yellow solid, which was sufficiently clean for use without

further purification. Yield 0.16 g, 85.3%. 1H{11B} NMR (CDCl3, 25 °C): δ 0.93 (d, JHH = 6.90 Hz, 12H,

CH3), 0.99 (d, JHH = 6.74 Hz, 12H, CH3), 1.38 (m, 3H, BH3). 3.47 (m, 4H, CHMe2), 6.70 (dq, JPH = 313.35

Hz, JHH = 6.65 Hz, 1H, PH), 7.08 (m, 4H, m-ArH), 7.28 (m, 2H, p-ArH). 13C{1H} NMR (CDCl3, 25 °C): δ

23.89 (CH3), 24.46 (CH3), 31.62 (CH), 124.88 (d, JPC = 7.90 Hz, Ar), 125.27 (d, JPC = 51.63 Hz, Ar), 131.45

(d, JPC = 1.86 Hz, Ar), 152.71 (d, JPC = 8.48 Hz, Ar). 11B{1H} NMR (CDCl3, 25 °C): δ -32.1 (s, br). 31P{1H}

NMR (CDCl3, 25 °C): δ -33.9 (s, br).

Ph2PH (25)

Solid sodium (4.09 g, 178.0 mmol) was added in portions to NH3(l) (200 mL) and stirred for 10 min. To

the resulting solution, Ph3P (23.3 g, 88.9 mmol) was added and the mixture was stirred for 30 min

before pre-dried NH4Br (17.4 g, 178.0 mmol) was added. The organic material was extracted with

diethyl ether (4 x 30 mL). The volatiles were removed in vacuo to give a pale yellow mixture. The

mixture was distilled to give 25 as a colourless liquid at 80 °C (10-2 mmHg). Yield 12.30 g, 74.4%. 1H

NMR (CDCl3, 25 °C): δ 5.12 (d, JPH = 218.05 Hz, 1H, PH), 7.10 (m, 6H, ArH), 7.30 (m, 4H, ArH). 31P{1H}

NMR (CDCl3, 25 °C): δ -40.2 (s).

Ph2P(BH3)H (38)

To a solution of Ph2PH (7.5 g, 34 mmol) in THF (100 mL) was added a solution of BH3.SMe2 in THF (8.5

mL, 2.0 M, 17 mmol) and the solution was stirred for 1 h. The volatiles were removed in vacuo to

give 38 as a pale yellow solid, which was sufficiently clean for use without further purification. Yield

3.74 g, 55.0%. 1H{11B} NMR (CDCl3, 25 °C): δ 1.29 (d, JPH = 16.24 Hz, 3H, BH3), 6.31 (dq, JPH = 378.11, JHH

= 7.24 Hz, 1H, PH), 7.46 (m, 6H, ArH), 7.68 (m, 4H, ArH). 11B{1H} NMR (CDCl3, 25 °C): δ -40.2 (d, JPB =

45.8 Hz). 31P{1H} NMR (CDCl3, 25 °C): δ 1.2 (m, br).

37

[(Ph2P(BH3))3Sn]Li(THF) (41)

To a solution of Ph2PH (1.27 g, 6.83 mmol) in THF (30 mL) was added a solution of BH 3.SMe2 in THF

(4.1 mL, 1.68 M, 6.83 mmol) and the solution was stirred for 1 h. A solution of n-BuLi in hexanes (3.0

mL, 2.3 M, 6.83 mmol) was added and the mixture was stirred for 1 h. The resulting red solution was

added dropwise to a suspension of SnCl2 (0.43 g, 2.3 mmol) in THF (10 mL) at -78 °C. The resulting

yellow solution was warmed slowly to room temperature and the volatiles were removed in vacuo.

Toluene (20 mL) was added to the resulting solid to give a yellow solution with pale solids that were

removed by filtration. The filtrate was reduced to 10 mL and was stored at -25 °C overnight. Crystals

suitable for X-ray crystallography of 41 were obtained. Isolated yield: 0.82 g, 45.6%. 1H{11B} NMR

(THF-d8/toluene-d8, 25 °C): δ 1.54 (d, JPH = 9.1 Hz, 9H, BH3), 6.98 (m, 12H, o-ArH), 7.00 (m, 6H, p-ArH),

7.61 (m, m-ArH). 13C{1H} NMR (THF-d8/toluene-d8, 25 °C): δ 127.69 (m, Ar), 128.00 (Ar), 134.31 (m,

Ar), 136.67 (m, Ar). 7Li NMR (THF-d8/toluene-d8, 25 °C): -0.6 (s, br). 11B{1H} NMR (THF-d8/toluene-d8,

25 °C): δ -32.6 (m, br). 31P{1H} NMR (THF-d8/toluene-d8, 25 °C): δ -12.4 (s, br, JSnP = 1632 Hz). 119Sn{1H}

NMR (THF-d8/toluene-d8, 25 °C): δ -59 (q, JSnP = 1632 Hz).

Mes2P(BH3)CH2Ph (45)

To a solution of Mes2PH (1.44 g, 5.33 mmol) in THF (30 mL) was added a solution of BH3.SMe2 in THF

(3.2 mL, 1.68 M, 5.33 mmol) and the solution was stirred for 1 h. A solution of n-BuLi in hexanes (2.3

mL, 2.3 M, 5.33 mmol) was added and the mixture was stirred for 1 h. The resulting red solution was

added to a solution of Ph2CH2Br (0.91 g, 5.33 mmol) in THF (20 mL). The volatiles were removed in

vacuo to give a pale yellow solid which was extracted into dichloromethane (50 mL), filtered and

dried over molecular sieves. The solvent was removed in vacuo from the filtrate to give 45 as a pale

yellow solid. Yield 1.53 g, 76.7%. 1H{11B} NMR (CDCl3, 25 °C): δ 1.43 (d, JPH = 12.9 Hz, 3H, BH3), 2.16 (s,

12H, o-CH3), 2.26 (s, 6H, p-CH3), 3.95 (d, JPH = 11.03 Hz, 2H, CH2), 6.77 (s, m-ArH), 6.90 (d, JHH = 7.66

Hz, 2H, o-ArH), 7.04 (m, ArH), 7.13 (m, ArH). 13C{1H} NMR (CDCl3, 25°C): δ 21.04 (d, JPC = 1.13 Hz, CH3),

23.51 (d, JPC = 4.55 Hz, CH3), 37.25 (d, JPC = 29.96 Hz, CH2), 126.93 (d, JPC = 3.67 Hz, Ar), 127.52 (d, JPC =

3.19 Hz, Ar), 131.01 (d, JPC = 9.17 Hz, Ar), 131.38 (d, JPC = 4.59 Hz, Ar), 132.64 (d, JPC = 3.30 Hz, Ar),

140.18 (d, JPC = 2.25 Hz, Ar), 141.68 (Ar), 141.77 (Ar). 11B{1H} NMR (CDCl3, 25 °C): δ -30.1 (s, br). 31P{1H} NMR (CDCl3, 25°C): δ 17.9 (s, br).

38

References

1. D. M. Giolando, R. A. Jones, C. M. Nunn, J. M. Power and A. H. Cowley, polyhedron, 1988, 7, 1909-

1910.

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1614-1616.

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7. P. J. Davidson and M. F. Lappert, J. Chem. Soc., Chem. Commun., 1973, 9, 317.

8. H. Sakurai, C. Kabuto, R. Hirano, R. Yauchibara and M. Kira, J. Am. Chem. Soc., 1991, 113, 7785-

7787.

9. M. S. Hill, P. B. Hitchcock, D. Patel, J. D. Smith, S. Zhang and C. Eaborn, Organometallics, 2000, 19,

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11. R. W. Harrington, W. Clegg, C. Wills, W. Mcfarlane and K. Izod, Organometallics, 2008, 27, 4386-

4394.

12. R. W. Harrington, W. Clegg, C. Wills and K. Izod, Organometallics, 2009, 28, 2211-2217.

13. R. W. Harrington, W. Clegg, C. Wills and K. Izod, Organometallics, 2009, 28, 5661-5668.

14. S. Herold, A. Mezzetti, A. Albinati, F. Lianza, T. Gerfin, V. Gramlich and L. M. Venanzi, Inorg. Chim.

Acta., 1995, 235, 215-231.

15. S. J. Coles, M. B. Hursthouse, A. Gaumont and J. M. Brown, Chem. Commun., 1999, 1, 63-64.

16. C. Lepetit, L. Toupet, C. Alayrac, J. Lohier, E. Bernoud and I. Abdellah and A. Gaumont, Chem.

Commun., 2012, 48, 4088-4090.

17. R. L. Harlow, M. Kline and A. J. Arduengo, J. Am. Chem. Soc., 1991, 113, 361-363.

18. L. Nyulaszi and A. Fekete, J. Organomet. Chem., 2002, 643-644, 278-284.

39

19. E. Despagnet, H. Gornitzka, A. B. Rozhenko, W. W. Schoeller, D. Bourissou and G. Bertrand,

Angew. Chem., Int. Ed., 2002, 41, 2835-2837.

20. R. W. Harrington, W. Clegg, E. R. Clark, J. Stewart and K. Izod, Inorg. Chem., 2010, 49, 4698-4707.

21. R. W. Harrington, W. Clegg, I. Carr, B. V. Tyson, W. Mcfarlane and K. Izod, Organometallics, 2006,

25, 1135-1143.

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5621-5622.

23. B. Neumann, H. G. Stammler, A. Becker and P. Jutzi, Organometallics, 1991, 10, 1647-1648.

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5283-5294.

25. R. A. Bartlett, M. M. Olmstead, G. A. Sigel and P. P. Power, Inorg. Chem., 1987, 26, 1941-1946.

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27. K. Izod et al, unpublished.

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40

Acknowledgments

I would like to thank supervisor Dr Keith Izod and his postgraduate students Peter Evans and Claire

Jones for their invaluable help and advice, not to mention their patience and commitment to

furthering my understanding of all aspects within the project. I would also like to thank Dr Paul

Waddell for his time and expert knowledge of X-ray crystallography, and Richard Wardle for his

insightful discussions on all matters related to the project.

Supplementary Material

41

NMR Spectra

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

Figure S1. 1H NMR spectrum of Mes2PH, 24, in CDCl3.

42

-124-118-112-106-100-96-92-88-84-80-76-72-68f1 (ppm)

Figure S2. 31P{1H} NMR spectrum of Mes2PH, 24, in CDCl3.

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

Figure S3. 1H{11B} NMR spectrum of Mes2P(BH3)H, 29, in CDCl3.

43

0102030405060708090100110120130140150f1 (ppm)

Figure S4. 13C{1H} NMR spectrum of Mes2P(BH3)H, 29, in CDCl3.

-70-65-60-55-50-45-40-35-30-25-20-15-10-505f1 (ppm)

Figure S5. 11B{1H} NMR spectrum of Mes2P(BH3)H 29, in CDCl3.

44

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

Figure S6. 1H{11B} NMR spectrum of [Mes2P(BH3)]Li(THF)2, 26, in THF-d8/toluene-d8.

-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.53.03.5f1 (ppm)

Figure S7. 7Li NMR spectrum of [Mes2P(BH3)]Li(THF)2, 26, in THF-d8/toluene-d8.

45

-52-48-44-40-36-32-28-24-20-16-12-8-6-4f1 (ppm)

Figure S8. 11B{1H} NMR spectrum of [Mes2P(BH3)]Li(THF)2, 26, in THF-d8/toluene-d8.

0102030405060708090100110120130140150160170f1 (ppm)

Figure S9. 13C{1H} NMR spectrum of [Mes2P(BH3)]Li(THF)2, 26, in THF-d8/toluene-d8.

46

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

Figure S10. 1H{11B} NMR spectrum of [Mes2P(BH3)2]Li(THF)2, 32, in CDCl3.

-6.5-5.5-4.5-3.5-2.5-1.5-0.50.51.52.53.54.55.5f1 (ppm)

Figure S11. 7Li NMR spectrum of [Mes2P(BH3)2]Li(THF)2, 32, in CDCl3.

47

-80-70-60-50-40-30-20-10-505101520253035f1 (ppm)

Figure S12. 11B NMR spectrum of [Mes2P(BH3)2]Li(THF)2, 32, in CDCl3.

0102030405060708090100110120130140150160f1 (ppm)

Figure S13. 13C{1H} NMR spectrum of [Mes2P(BH3)2]Li(THF)2, 32, in CDCl3.

48

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

Figure S14. 1H{11B} NMR spectrum of Dipp2P(BH3)H, 36, in CDCl3.

-52-46-40-34-28-22-16-10-6-2024f1 (ppm)

Figure S15. 11B{1H} NMR spectrum of Dipp2P(BH3)H, 36, in CDCl3.

49

0102030405060708090100110120130140150160f1 (ppm)

Figure S16. 13C{1H} NMR spectrum of Dipp2P(BH3)H, 36, in CDCl3.

-150-140-130-120-110-100-90-80-70-60-50-40-30-20-1001020f1 (ppm)

Figure S17. 31P{1H} NMR spectrum of Dipp2P(BH3)H, 36, in CDCl3.

50

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

Figure S18. 1H NMR spectrum of Ph2PH, 25, in CDCl3.

-150-130-110-90-80-70-60-50-40-30-20-1001020f1 (ppm)

Figure S19. 31P NMR spectrum of Ph2PH, 25, in CDCl3.

51

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

Figure S20. 1H{11B} NMR spectrum of Ph2P(BH3)H, 38, in CDCl3.

-70-64-58-52-46-40-34-28-22-16-10f1 (ppm)

Figure S21. 11B{1H} NMR spectrum of Ph2P(BH3)H, 38, in CDCl3.

52

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

Figure S22. 1H{11B} NMR spectrum of [(Ph2P(BH3))3Sn]Li(THF), 41, in THF-d8/toluene-d8.

-4.0-3.4-2.8-2.2-1.6-1.0-0.40.00.40.81.21.6f1 (ppm)

Figure S23. 7Li NMR spectrum of [(Ph2P(BH3))3Sn]Li(THF), 41, in THF-d8/toluene-d8.

53

-47-41-35-29-23-17f1 (ppm)

Figure S24. 11B{1H} NMR spectrum of [(Ph2P(BH3))3Sn]Li(THF), 41, in THF-d8/toluene-d8.

05152535455565758595105115125135f1 (ppm)

Figure S25. 13C{1H} NMR spectrum of [(Ph2P(BH3))3Sn]Li(THF), 41, in THF-d8/toluene-d8.

54

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

Figure S26. 1H{11B} NMR spectrum of Mes2P(BH3)CH2Ph, 45, in CDCl3.

-75-70-65-60-55-50-45-40-35-30-25-20-15-10-5051015f1 (ppm)

Figure S27. 11B NMR spectrum of Mes2P(BH3)CH2Ph, 45, in CDCl3.

55

05152535455565758595110125140f1 (ppm)

Figure S28. 13C{1H} NMR spectrum of Mes2P(BH3)CH2Ph, 45, in CDCl3.

-70-60-50-40-30-20-100102030405060708090f1 (ppm)

Figure S29. 31P NMR spectrum of Mes2P(BH3)CH2Ph, 45, in CDCl3.

56

-55-50-45-40-35-30-25-20-15f1 (ppm)

Figure S30. 11B{1H} NMR spectrum of [Ph2P(BH3)]Li, 28, reaction mixture after one hour in THF.

-64-60-56-52-48-44-40-36-32-28-24-20f1 (ppm)

Figure S31. 11B{1H} NMR spectrum of [Ph2P(BH3)2]Li, 39, reaction mixture after one hour in THF.

57

-105-95-85-75-65-55-45-35-25-15-50515f1 (ppm)

Figure S32. 31P NMR spectrum of [Mes2P(BH3)]Li(THF)2, 26, and the corresponding hydrolysis products, 32 and 24 after

three days in THF-d8/toluene-d8.

58

X-ray Crystallography Data[Mes2P(BH3)]Li(THF)2

Table 1 : Crystal data and structure refinement for [Mes2P(BH3)]Li(THF)2 (26)

Identification code kji160011 Empirical formula C52H82B2Li2O4P2 Formula weight 868.61 Temperature/K 150.0(2) Crystal system triclinic Space group P-1 a/Å 9.8199(4) b/Å 11.2010(3) c/Å 13.0590(4) α/° 72.190(3) β/° 69.572(4) γ/° 74.325(3) Volume/Å3 1259.87(9) Z 1 ρcalcg/cm3 1.145 μ/mm-1 1.095 F(000) 472.0 Crystal size/mm3 0.27 × 0.21 × 0.15 Radiation CuKα (λ = 1.54184) 2Θ range for data collection/° 7.43 to 133.902

Index ranges -11 ≤ h ≤ 11, -13 ≤ k ≤ 13, -15 ≤ l ≤ 15 Reflections collected 34155 Independent reflections 4453 [Rint = 0.0474, Rsigma = 0.0244] Data/restraints/parameters 4453/0/295 Goodness-of-fit on F2 1.057 Final R indexes [I>=2σ (I)] R1 = 0.0363, wR2 = 0.0883 Final R indexes [all data] R1 = 0.0466, wR2 = 0.0953 Largest diff. peak/hole / e Å-3 0.33/-0.23

Table 2 Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for kji160011. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.Atomx y z U(eq)P1 5205.0(5) 7072.2(4) 3281.7(3) 26.74(12)O1 6045.9(14) 5700.9(11) 7341.4(10) 36.8(3)O2 8268.5(13) 3887.7(11) 5756.4(9) 34.5(3)C1 7037.3(18) 7327.2(15) 2287.7(13) 27.2(3)C2 7958.7(19) 6313.2(15) 1799.1(13) 29.6(4)

59

C3 9380.5(19) 6436.6(16) 1098.0(14) 33.7(4)C4 9947(2) 7533.2(17) 854.5(13) 34.3(4)C5 9040(2) 8519.9(16) 1341.8(14) 34.2(4)C6 7611.3(19) 8441.3(15) 2051.4(13) 30.0(4)C7 7448(2) 5077.7(16) 2010.3(15) 36.7(4)C8 11494(2) 7643.4(19) 108.6(16) 43.5(5)C9 6741(2) 9561.8(16) 2557.4(15) 36.9(4)C10 3900.1(18) 8570.2(14) 2952.3(13) 26.1(3)C11 3709.9(19) 8956.9(15) 1861.8(13) 28.4(4)C12 2584.6(19) 9947.9(15) 1615.9(14) 31.4(4)C13 1584.4(19) 10587.4(15) 2414.4(14) 32.1(4)C14 1792.4(19) 10222.8(15) 3472.0(14) 31.1(4)C15 2923.9(18) 9253.9(14) 3756.5(13) 28.1(3)C16 4699(2) 8301.3(17) 937.6(14) 36.2(4)C17 329(2) 11623.1(18) 2148.8(17) 44.7(5)C18 3040(2) 9020.2(17) 4928.5(14) 38.8(4)C19 5408(2) 7020.5(17) 7364.3(16) 42.1(5)C20 5671(2) 7246.0(18) 8352.1(17) 45.9(5)C21 6853(3) 6142(2) 8646.7(18) 53.7(5)C22 6557(3) 5105.6(19) 8309.9(18) 56.4(6)C23 9134(2) 3078.8(16) 6495.8(15) 36.5(4)C24 10434(2) 2321.5(17) 5781.8(16) 41.8(4)C25 10638(2) 3203.6(16) 4617.6(15) 36.9(4)C26 9061(2) 3776.3(18) 4618.9(15) 39.5(4)B1 5684(2) 6669.5(19) 4706.0(16) 34.2(4)Li1 6208(3) 4838(3) 6180(2) 32.2(6)

 

Table 3 Anisotropic Displacement Parameters (Å2×103) for kji160011. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].Atom U11 U22 U33 U23 U13 U12

P1 28.2(2) 22.5(2) 26.7(2) -4.95(15) -4.28(16) -5.93(16)O1 46.9(8) 29.8(6) 35.4(6) -12.4(5) -14.0(6) -1.7(5)O2 31.8(7) 33.5(6) 31.9(6) -6.1(5) -6.2(5) -2.0(5)C1 28.7(9) 27.7(8) 23.2(8) -2.9(6) -7.0(6) -6.3(6)C2 30.3(9) 30.6(8) 26.1(8) -4.9(6) -7.8(7) -5.2(7)C3 31.3(10) 37.3(9) 29.1(8) -7.9(7) -7.6(7) -2.4(7)C4 29.9(10) 43.8(10) 25.2(8) 0.3(7) -8.6(7) -9.1(8)C5 36.5(10) 34.0(9) 31.5(9) 1.4(7) -11.9(7) -13.3(7)C6 32.4(10) 29.3(8) 27.6(8) -1.6(6) -10.2(7) -8.3(7)C7 35.4(10) 31.4(9) 40.1(10) -14.4(7) -3.0(8) -4.7(7)C8 33.3(11) 52.5(11) 36.9(10) 0.1(8) -6.7(8) -11.9(8)C9 40.2(11) 28.6(9) 42.9(10) -7.4(7) -9.9(8) -12.0(7)C10 28.8(9) 23.9(7) 26.3(8) -5.0(6) -6.4(6) -9.2(6)

60

C11 33.2(9) 27.9(8) 26.5(8) -6.0(6) -6.3(7) -12.7(7)C12 36.5(10) 32.9(8) 27.6(8) -1.2(7) -12.5(7) -13.6(7)C13 32.5(10) 27.8(8) 37.0(9) -4.4(7) -11.9(7) -8.4(7)C14 31.6(10) 28.6(8) 31.9(9) -10.0(7) -5.4(7) -5.3(7)C15 32.4(9) 25.2(8) 27.0(8) -5.3(6) -8.0(7) -7.6(7)C16 41.8(11) 42.5(10) 26.5(8) -11.0(7) -9.1(8) -8.9(8)C17 41.3(12) 43(1) 49.0(11) -7.0(8) -20.1(9) -1.6(8)C18 43.3(11) 39.4(10) 29.9(9) -13.2(7) -10.0(8) 3.2(8)C19 49.4(12) 32.3(9) 44.7(11) -17.3(8) -13.9(9) 2.0(8)C20 54.7(13) 41.1(10) 46.4(11) -19.7(9) -12.7(9) -7.5(9)C21 59.4(15) 62.6(13) 45.2(12) -17.5(10) -20.3(10) -8.8(11)C22 84.0(17) 42.4(11) 44.8(11) -14.0(9) -31.5(11) 6.7(11)C23 36.2(10) 34.6(9) 35.6(9) -1.5(7) -11.9(8) -7.4(7)C24 34.1(11) 36.4(10) 48.4(11) -5.3(8) -10.9(8) -2.7(8)C25 32.9(10) 35.1(9) 40.6(10) -12.8(8) -3.9(8) -7.2(7)C26 38.2(11) 45.8(10) 33.8(9) -13.2(8) -8.3(8) -5.0(8)B1 34.9(12) 32.8(10) 27.4(10) -0.7(8) -8.5(8) -2.4(8)Li1 35.5(16) 28.2(14) 31.4(14) -6.5(11) -9.1(12) -4.8(11)

 

Table 4 Bond Lengths for kji160011.Atom Atom Length/Å   Atom Atom Length/ÅP1 C1 1.8505(16)   C6 C9 1.509(2)P1 C10 1.8504(16)   C10 C11 1.420(2)P1 B1 1.967(2)   C10 C15 1.415(2)P1 Li11 2.645(3)   C11 C12 1.387(2)O1 C19 1.446(2)   C11 C16 1.509(2)O1 C22 1.429(2)   C12 C13 1.388(2)O1 Li1 1.976(3)   C13 C14 1.387(2)O2 C23 1.448(2)   C13 C17 1.505(2)O2 C26 1.443(2)   C14 C15 1.393(2)O2 Li1 1.987(3)   C15 C18 1.512(2)C1 C2 1.415(2)   C19 C20 1.504(3)C1 C6 1.412(2)   C20 C21 1.506(3)C2 C3 1.393(2)   C21 C22 1.487(3)C2 C7 1.513(2)   C23 C24 1.512(3)C3 C4 1.388(2)   C24 C25 1.518(2)C4 C5 1.386(3)   C25 C26 1.507(3)C4 C8 1.506(2)   B1 Li1 2.426(3)C5 C6 1.395(2)   Li1 P11 2.645(3)

11-X,1-Y,1-Z

 

61

Table 5 Bond Angles for kji160011.Atom Atom Atom Angle/˚   Atom Atom Atom Angle/˚C1 P1 B1 99.22(8)   C15 C10 C11 117.34(15)C1 P1 Li11 130.60(8)   C10 C11 C16 121.70(15)C10 P1 C1 106.01(7)   C12 C11 C10 120.64(15)C10 P1 B1 117.47(8)   C12 C11 C16 117.66(14)C10 P1 Li11 107.43(8)   C11 C12 C13 122.30(15)B1 P1 Li11 96.42(9)   C12 C13 C17 121.70(16)C19 O1 Li1 126.68(13)   C14 C13 C12 116.81(16)C22 O1 C19 108.47(13)   C14 C13 C17 121.49(16)C22 O1 Li1 124.85(13)   C13 C14 C15 123.21(15)C23 O2 Li1 127.90(13)   C10 C15 C18 123.91(15)C26 O2 C23 109.06(13)   C14 C15 C10 119.61(15)C26 O2 Li1 122.55(13)   C14 C15 C18 116.46(14)C2 C1 P1 118.13(12)   O1 C19 C20 106.45(15)C6 C1 P1 123.70(12)   C19 C20 C21 104.74(15)C6 C1 C2 118.00(15)   C22 C21 C20 102.23(17)C1 C2 C7 121.90(15)   O1 C22 C21 106.34(16)C3 C2 C1 120.05(15)   O2 C23 C24 106.10(14)C3 C2 C7 118.05(14)   C23 C24 C25 102.59(14)C4 C3 C2 122.24(16)   C26 C25 C24 101.77(14)C3 C4 C8 121.56(17)   O2 C26 C25 105.72(14)C5 C4 C3 117.36(16)   P1 B1 Li1 139.76(12)C5 C4 C8 121.07(16)   O1 Li1 P11 119.94(13)C4 C5 C6 122.56(16)   O1 Li1 O2 107.33(15)C1 C6 C9 122.34(15)   O1 Li1 B1 100.33(12)C5 C6 C1 119.78(15)   O2 Li1 P11 98.67(11)C5 C6 C9 117.88(14)   O2 Li1 B1 112.84(14)C11 C10 P1 117.70(11)   B1 Li1 P11 117.82(13)C15 C10 P1 124.28(12)          

11-X,1-Y,1-Z

 

Table 6 Torsion Angles for kji160011.A B C D Angle/˚   A B C D Angle/˚

P1 C1 C2 C3 -176.23(12)   C11 C12 C13 C142.4(2)

P1 C1 C2 C7 3.9(2)   C11 C12 C13 C17-177.31(16)P1 C1 C6 C5 176.13(12)   C12 C13 C14 C15-0.9(2)P1 C1 C6 C9 -2.8(2)   C13 C14 C15 C10-1.8(2)P1 C10 C11 C12169.51(12)   C13 C14 C15 C18177.07(16)P1 C10 C11 C16-9.6(2)   C15 C10 C11 C12-1.5(2)

P1 C10 C15 C14-167.45(12)   C15 C10 C11 C16179.42(14)

62

P1 C10 C15 C1813.8(2)   C16 C11 C12 C13177.92(15)O1 C19 C20 C2116.5(2)   C17 C13 C14 C15178.80(16)O2 C23 C24 C2528.08(18)   C19 O1 C22 C21-24.9(2)C1 P1 C10 C1161.60(14)   C19 C20 C21 C22-30.5(2)

C1 P1 C10 C15-128.10(14)   C20 C21 C22 O1 34.3(2)

C1 C2 C3 C4 0.2(3)   C22 O1 C19 C204.9(2)C2 C1 C6 C5 0.9(2)   C23 O2 C26 C25-17.40(18)

C2 C1 C6 C9 -178.03(15)   C23 C24 C25 C26-37.56(18)

C2 C3 C4 C5 0.2(2)   C24 C25 C26 O2 34.27(17)C2 C3 C4 C8 179.08(16)   C26 O2 C23 C24-6.96(18)C3 C4 C5 C6 0.0(2)   B1 P1 C1 C2 98.76(14)C4 C5 C6 C1 -0.5(2)   B1 P1 C1 C6 -76.48(15)C4 C5 C6 C9 178.43(16)   B1 P1 C10 C11171.31(12)C6 C1 C2 C3 -0.7(2)   B1 P1 C10 C15-18.39(17)C6 C1 C2 C7 179.46(15)   Li11 P1 C1 C2 -8.00(18)C7 C2 C3 C4 180.00(16)   Li11 P1 C1 C6 176.76(13)

C8 C4 C5 C6 -178.91(16)   Li11 P1 C10 C11-81.51(14)

C10 P1 C1 C2 -139.04(13)   Li11 P1 C10 C1588.79(15)

C10 P1 C1 C6 45.72(15)   Li1 O1 C19 C20-174.92(16)C10 C11 C12 C13-1.2(2)   Li1 O1 C22 C21154.89(17)C11 C10 C15 C142.9(2)   Li1 O2 C23 C24165.03(15)

C11 C10 C15 C18-175.85(15)   Li1 O2 C26 C25170.09(14)

11-X,1-Y,1-Z

 

Table 7 Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for kji160011.Atom x y z U(eq)H3 9983 5747 776 40H5 9407 9279 1186 41H7A 7218 4669 2815 55H7B 8233 4507 1587 55H7C 6562 5256 1766 55H8A 12083 7728 545 65H8B 11462 8396 -516 65H8C 11945 6878 -189 65H9A 6002 10048 2166 55H9B 7412 10113 2480 55H9C 6243 9253 3356 55H12 2495 10198 875 38

63

H14 1131 10655 4030 37H16A5710 8444 743 54H16B 4339 8650 274 54H16C 4691 7384 1196 54H17A626 12066 1354 67H17B 76 12233 2617 67H17C -534 11245 2302 67H18A2962 8133 5326 58H18B 2239 9594 5337 58H18C 3995 9182 4882 58H19A4335 7184 7452 50H19B 5885 7593 6658 50H20A4757 7258 8992 55H20B 6011 8066 8148 55H21A7854 6332 8218 64H21B 6751 5920 9461 64H22A7470 4468 8128 68H22B 5796 4671 8926 68H23A8537 2501 7124 44H23B 9480 3602 6811 44H24A10208 1504 5802 50H24B 11326 2146 6032 50H25A11199 3866 4514 44H25B 11149 2724 4024 44H26A9005 4625 4090 47H26B 8643 3217 4396 47H1A 4720(20) 6349(19) 5464(17) 51H1B 6590(20) 5800(20) 4587(16) 51H1C 6120(20) 7440(20) 4824(17) 51

64

[Mes2P(BH3)2]Li(THF)2 (32)

Table 1 : Crystal data and structure refinement for [Mes2P(BH3)2]Li(THF)2

Identification code kji160019_sa Empirical formula C26H44B2LiO2P Formula weight 448.14 Temperature/K 150.0(2) Crystal system monoclinic Space group P21/c a/Å 8.85840(10) b/Å 17.3236(2) c/Å 17.7774(2) α/° 90 β/° 93.8780(10) γ/° 90 Volume/Å3 2721.86(5) Z 4 ρcalcg/cm3 1.094 μ/mm-1 1.020 F(000) 976.0 Crystal size/mm3 0.25 × 0.21 × 0.15 Radiation CuKα (λ = 1.54184) 2Θ range for data collection/° 7.132 to 133.778

Index ranges -10 ≤ h ≤ 10, -20 ≤ k ≤ 20, -18 ≤ l ≤ 21 Reflections collected 38178 Independent reflections 4841 [Rint = 0.0421, Rsigma = 0.0238] Data/restraints/parameters 4841/7/328 Goodness-of-fit on F2 1.041 Final R indexes [I>=2σ (I)] R1 = 0.0423, wR2 = 0.1114 Final R indexes [all data] R1 = 0.0484, wR2 = 0.1171 Largest diff. peak/hole / e Å-3 0.30/-0.28

Table 2 Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for kji160019_sa. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.Atomx y z U(eq)P1 5440.3(4) 1993.3(2) 3368.2(2) 25.81(13)O1 8765.4(14) 3325.6(8) 4953.0(7) 43.9(3)O2 9147.2(15) 3860.0(8) 3325.3(7) 47.4(3)C1 4192.2(17) 1521.0(9) 4016.6(8) 27.4(3)

65

C2 4752.5(18) 1188.2(9) 4704.7(9) 29.3(3)C3 3743(2) 886.0(9) 5191.7(9) 32.6(4)C4 2192(2) 913.5(10) 5040.9(10) 35.4(4)C5 1651.9(19) 1235.9(10) 4364.3(10) 35.0(4)C6 2610.8(18) 1544.2(9) 3850.6(9) 30.7(3)C7 6412(2) 1164.5(11) 4958.5(10) 38.0(4)C8 1141(2) 634.9(12) 5618.3(11) 47.0(5)C9 1869.1(19) 1902.7(11) 3143.6(10) 37.9(4)C10 4839.8(16) 1597.3(9) 2431.1(9) 27.0(3)C11 4502.6(18) 2071.2(10) 1799.6(10) 33.3(4)C12 4042.5(19) 1736.9(11) 1109.4(10) 38.2(4)C13 3911(2) 947.3(12) 1016.4(10) 40.2(4)C14 4306(2) 483.6(10) 1633.3(10) 37.9(4)C15 4769.8(17) 788.6(9) 2336.5(9) 30.8(3)C16 4616(3) 2937.1(11) 1832.6(11) 49.1(5)C17 3334(3) 598.5(15) 274.4(11) 60.6(6)C18 5151(2) 218.9(9) 2963.4(10) 36.7(4)C19 7943(3) 3624.4(16) 5550.9(12) 63.7(6)C21 9947(3) 2928(2) 6101.7(16) 88.6(10)C22 9985(3) 2857.4(18) 5278.4(14) 68.2(7)B1 5202(2) 3087.6(11) 3627.2(12) 35.8(4)B2 7638(2) 1834.8(11) 3422.2(11) 32.3(4)Li1 7947(3) 3186.3(19) 3909.5(17) 41.2(7)C20A8389(4) 3152(2) 6229.5(16) 65.3(8)C23A8696(4) 4151(2) 2573.6(19) 47.9(8)C24A9767(4) 4838(3) 2505(4) 63.2(13)C25A11234(5) 4570(3) 2946(3) 66.9(11)C26A10618(3) 4146(2) 3584(2) 50.1(8)C20B 9050(17) 3515(9) 6269(7) 65.3(8)C23B 9080(13) 3916(7) 2524(6) 47.9(8)C24B 9238(17) 4789(9) 2384(12) 63.2(13)C25B 10780(17) 4791(9) 2896(9) 66.9(11)C26B 10196(11) 4434(6) 3586(6) 50.1(8)

 

Table 3 Anisotropic Displacement Parameters (Å2×103) for kji160019_sa. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].Atom U11 U22 U33 U23 U13 U12

P1 23.0(2) 26.9(2) 27.2(2) 0.33(14) -0.79(15) -0.26(14)O1 42.5(7) 54.8(8) 33.7(6) -3.4(5) -1.7(5) -0.6(6)O2 45.5(7) 56.1(8) 39.8(7) 7.1(6) -4.0(6) -16.2(6)C1 27.6(8) 27.5(7) 27.1(7) -2.0(6) 1.4(6) 0.4(6)C2 33.5(8) 27.1(8) 26.8(7) -3.6(6) -1.1(6) 1.0(6)C3 43.1(9) 30.0(8) 24.7(7) -1.0(6) 1.0(7) 0.4(7)

66

C4 40.8(9) 31.9(8) 34.5(9) -2.9(7) 9.5(7) -1.8(7)C5 27.2(8) 38.6(9) 39.6(9) -2.0(7) 5.6(7) -0.1(7)C6 28.4(8) 33.1(8) 30.7(8) -1.3(6) 1.7(6) 0.5(6)C7 38.2(9) 41.5(9) 33.2(9) 5.2(7) -6.7(7) 0.6(7)C8 49.4(11) 49.9(11) 43.6(10) 3.0(8) 15.8(9) -3.2(9)C9 24.5(8) 49.8(10) 39.1(9) 7.4(8) -0.7(7) 0.9(7)C10 22.7(7) 30.7(8) 27.4(7) 1.2(6) 0.9(6) -1.3(6)C11 28.3(8) 37.6(9) 33.6(8) 5.6(7) -1.1(6) -1.2(6)C12 33.3(9) 50.7(10) 29.8(8) 9.5(7) -3.2(7) -2.4(7)C13 37.2(9) 52.9(11) 29.8(9) -2.9(7) -1.7(7) -6.7(8)C14 40.7(9) 35.9(9) 37.1(9) -4.5(7) 1.9(7) -5.5(7)C15 29.0(8) 33.3(8) 29.9(8) -0.8(6) 1.3(6) -2.3(6)C16 67.0(13) 38(1) 40.8(10) 13.8(8) -6.8(9) -1.7(9)C17 69.4(14) 75.4(15) 35.5(10) -8.7(10) -8.7(10) -14.1(12)C18 46.8(10) 26.4(8) 36.5(9) 0.1(7) -0.9(7) 1.1(7)C19 73.2(15) 76.0(16) 41.6(11) -10.1(10) 1.9(11) 22.2(12)C21 70.1(17) 138(3) 56.3(15) 23.7(16) -7.2(13) 20.3(18)C22 46.2(12) 98.4(19) 57.4(13) -16.3(13) -15.3(10) 20.7(12)B1 32.1(10) 29.6(9) 45.2(11) -5.6(8) -0.7(8) 0.3(7)B2 23.1(8) 37.7(10) 35.8(10) -1.7(8) -0.3(7) 0.2(7)Li1 39.7(16) 46.1(17) 37.5(16) 2.6(13) -0.8(13) -7.3(13)C20A72(2) 81(2) 43.4(14) 6.6(14) 9.9(14) -7.5(16)C23A39(2) 62(2) 42.5(12) 8.4(15) 5.3(13) 9.1(13)C24A56(3) 70.2(18) 66(3) 19.0(17) 24(3) 6(2)C25A51(3) 63(3) 89(2) 1(2) 27(2) -5.0(16)C26A32.7(17) 62(2) 55.1(14) 0.7(17) -3.7(14) -6.6(13)C20B 72(2) 81(2) 43.4(14) 6.6(14) 9.9(14) -7.5(16)C23B 39(2) 62(2) 42.5(12) 8.4(15) 5.3(13) 9.1(13)C24B 56(3) 70.2(18) 66(3) 19.0(17) 24(3) 6(2)C25B 51(3) 63(3) 89(2) 1(2) 27(2) -5.0(16)C26B 32.7(17) 62(2) 55.1(14) 0.7(17) -3.7(14) -6.6(13)

 

Table 4 Bond Lengths for kji160019_sa.Atom Atom Length/Å   Atom Atom Length/ÅP1 C1 1.8419(16)   C10 C15 1.412(2)P1 C10 1.8464(16)   C11 C12 1.393(2)P1 B1 1.9655(19)   C11 C16 1.504(3)P1 B2 1.9619(18)   C12 C13 1.382(3)O1 C19 1.426(3)   C13 C14 1.385(3)O1 C22 1.440(3)   C13 C17 1.508(3)O1 Li1 1.960(3)   C14 C15 1.393(2)O2 Li1 1.929(3)   C15 C18 1.510(2)O2 C23A1.458(3)   C19 C20A1.489(4)

67

O2 C26A1.440(3)   C19 C20B 1.567(12)O2 C23B 1.425(10)   C21 C22 1.471(4)O2 C26B 1.418(10)   C21 C20A1.466(4)C1 C2 1.412(2)   C21 C20B 1.336(13)C1 C6 1.413(2)   B1 Li1 2.455(4)C2 C3 1.388(2)   B2 Li1 2.505(4)C2 C7 1.509(2)   C23A C24A1.533(5)C3 C4 1.383(3)   C24A C25A1.543(5)C4 C5 1.382(2)   C25A C26A1.486(5)C4 C8 1.511(2)   C23B C24B 1.540(15)C5 C6 1.395(2)   C24B C25B 1.589(14)C6 C9 1.512(2)   C25B C26B 1.497(14)C10 C11 1.406(2)        

 

Table 5 Bond Angles for kji160019_sa.Atom Atom Atom Angle/˚   Atom Atom Atom Angle/˚C1 P1 C10 104.54(7)   C12 C11 C10 119.62(16)C1 P1 B1 101.74(8)   C12 C11 C16 117.64(15)C1 P1 B2 122.87(8)   C13 C12 C11 122.31(16)C10 P1 B1 122.73(8)   C12 C13 C14 117.68(16)C10 P1 B2 102.51(7)   C12 C13 C17 121.47(18)B2 P1 B1 104.20(8)   C14 C13 C17 120.84(18)C19 O1 C22 108.18(16)   C13 C14 C15 122.27(16)C19 O1 Li1 125.12(16)   C10 C15 C18 123.71(14)C22 O1 Li1 122.00(16)   C14 C15 C10 119.40(15)C23AO2 Li1 125.13(19)   C14 C15 C18 116.88(15)C26AO2 Li1 123.74(18)   O1 C19 C20A106.5(2)C26AO2 C23A111.1(2)   O1 C19 C20B 103.9(5)C23B O2 Li1 126.3(5)   C20A C21 C22 105.2(2)C26B O2 Li1 128.4(5)   C20B C21 C22 109.8(6)C26B O2 C23B 105.1(7)   O1 C22 C21 106.6(2)C2 C1 P1 122.20(12)   P1 B1 Li1 89.70(11)C2 C1 C6 118.57(14)   P1 B2 Li1 88.33(10)C6 C1 P1 119.04(12)   O1 Li1 B1 119.99(15)C1 C2 C7 123.26(14)   O1 Li1 B2 117.85(15)C3 C2 C1 119.40(15)   O2 Li1 O1 104.65(15)C3 C2 C7 117.30(14)   O2 Li1 B1 120.42(16)C4 C3 C2 122.64(15)   O2 Li1 B2 115.50(15)C3 C4 C8 120.48(16)   B1 Li1 B2 77.33(11)C5 C4 C3 117.62(15)   C21 C20AC19 102.8(2)C5 C4 C8 121.84(16)   O2 C23AC24A102.1(3)C4 C5 C6 122.30(15)   C23A C24AC25A103.3(4)C1 C6 C9 123.67(14)   C26A C25AC24A101.4(3)

68

C5 C6 C1 119.45(15)   O2 C26AC25A107.3(3)C5 C6 C9 116.87(14)   C21 C20B C19 105.1(8)C11 C10 P1 122.41(12)   O2 C23B C24B 103.4(11)C11 C10 C15 118.62(14)   C23B C24B C25B 89.6(12)C15 C10 P1 118.92(11)   C26B C25B C24B 97.9(12)C10 C11 C16 122.75(16)   O2 C26B C25B 106.1(10)

 

Table 6 Torsion Angles for kji160019_sa.A B C D Angle/˚   A B C D Angle/˚P1 C1 C2 C3 175.78(12)   C13 C14 C15 C18 179.31(16)P1 C1 C2 C7 -2.1(2)   C15 C10 C11 C12 3.0(2)

P1 C1 C6 C5 -175.52(12)   C15 C10 C11 C16 -

177.03(16)P1 C1 C6 C9 3.2(2)   C16 C11 C12 C13 179.58(18)

P1 C10 C11 C12 -179.43(12)   C17 C13 C14 C15 -

176.72(18)P1 C10 C11 C16 0.6(2)   C19 O1 C22 C21 -4.1(3)P1 C10 C15 C14 179.46(12)   C22 O1 C19 C20A-16.4(3)P1 C10 C15 C18 0.4(2)   C22 O1 C19 C20B 17.2(7)O1 C19 C20A C21 30.3(3)   C22 C21 C20A C19 -32.3(4)O1 C19 C20B C21 -25.5(11)   C22 C21 C20B C19 23.6(11)O2 C23A C24A C25A34.2(4)   B1 P1 C1 C2 -98.30(14)O2 C23B C24B C25B 55.8(12)   B1 P1 C1 C6 76.64(14)C1 P1 C10 C11 129.53(13)   B1 P1 C10 C11 14.91(16)

C1 P1 C10 C15 -52.90(13)   B1 P1 C10 C15 -167.52(12)

C1 C2 C3 C4 -1.7(2)   B2 P1 C1 C2 17.34(16)

C2 C1 C6 C5 -0.4(2)   B2 P1 C1 C6 -167.72(12)

C2 C1 C6 C9 178.37(15)   B2 P1 C10 C11 -101.27(14)

C2 C3 C4 C5 2.1(2)   B2 P1 C10 C15 76.30(13)

C2 C3 C4 C8 -174.98(16)   Li1 O1 C19 C20A139.5(2)

C3 C4 C5 C6 -1.6(3)   Li1 O1 C19 C20B 173.1(7)C4 C5 C6 C1 0.8(3)   Li1 O1 C22 C21 -160.9(2)

C4 C5 C6 C9 -178.04(16)   Li1 O2 C23A C24A161.8(3)

C6 C1 C2 C3 0.8(2)   Li1 O2 C26A C25A173.9(2)

C6 C1 C2 C7 -177.07(15)   Li1 O2 C23B C24B 140.4(7)

C7 C2 C3 C4 176.31(15)   Li1 O2 C26B C25B -179.0(6)C8 C4 C5 C6 175.40(16)   C20A C21 C22 O1 23.3(4)C10 P1 C1 C2 133.06(13)   C23A O2 C26A C25A-6.4(4)C10 P1 C1 C6 -52.00(14)   C23A C24A C25A C26A-38.0(5)C10 C11 C12 C13 -0.4(3)   C24A C25A C26A O2 27.5(4)

69

C11 C10 C15 C14 -2.9(2)   C26A O2 C23A C24A-17.8(3)C11 C10 C15 C18 178.09(15)   C20B C21 C22 O1 -13.5(9)C11 C12 C13 C14 -2.2(3)   C23B O2 C26B C25B -2.8(9)C11 C12 C13 C17 176.82(18)   C23B C24B C25B C26B -54.3(12)C12 C13 C14 C15 2.3(3)   C24B C25B C26B O2 38.4(12)C13 C14 C15 C10 0.2(3)   C26B O2 C23B C24B -35.9(10)

 

Table 7 Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for kji160019_sa.Atom x y z U(eq)H3 4126 656 5637 39H5 613 1248 4247 42H7A 6967 934 4571 57H7B 6551 865 5412 57H7C 6773 1680 5053 57H8A 1359 105 5739 71H8B 112 680 5416 71H8C 1284 943 6066 71H9A 2358 2383 3044 57H9B 818 1994 3212 57H9C 1960 1558 2726 57H12 3816 2056 697 46H14 4260 -50 1576 45H16A3963 3131 2199 74H16B 4315 3149 1347 74H16C 5641 3084 1973 74H17A2248 607 237 91H17B 3681 75 246 91H17C 3706 892 -132 91H18A6053 382 3248 55H18B 5311 -282 2752 55H18C 4330 194 3289 55H19A6863 3584 5426 76H19B 8195 4163 5641 76H19C 7012 3339 5597 76H19D7702 4165 5470 76H21A10201 2440 6346 106H21B 10655 3318 6296 106H21C 9570 2452 6308 106H21D10961 3016 6325 106H22A10947 3038 5116 82H22B 9849 2323 5125 82H1A 5580(30) 3054(13) 4268(13) 54

70

H1B 4020(30) 3306(13) 3556(13) 54H1C 6010(30) 3449(13) 3305(13) 54H2A 8130(20) 2069(13) 3970(12) 48H2B 8000(20) 1250(13) 3329(12) 48H2C 7910(20) 2215(13) 2935(12) 48H20A8348 3453 6688 78H20B 7743 2702 6260 78H23A7646 4314 2537 58H23B 8845 3765 2190 58H24A9365 5299 2727 76H24B 9942 4942 1981 76H25A11825 4234 2644 80H25B 11850 5005 3122 80H26A11280 3720 3739 60H26B 10536 4488 4012 60H20C 9638 3979 6373 78H20D8493 3393 6705 78H23C 8123 3723 2302 58H23D9899 3631 2319 58H24C 8445 5096 2586 76H24D9359 4920 1861 76H25C 11552 4477 2684 80H25D11163 5309 2989 80H26C 11018 4205 3898 60H26D9703 4820 3880 60

 

Table 8 Atomic Occupancy for kji160019_sa.AtomOccupancy   AtomOccupancy   AtomOccupancyH19A

0.8238   H19B 0.8238   H19C 0.1762

H19D

0.1762   H21A 0.8238   H21B 0.8238

H21C 0.1762   H21D 0.1762   C20A 0.8238H20A

0.8238   H20B 0.8238   C23A 0.7342

H23A

0.7342   H23B 0.7342   C24A 0.7342

H24A

0.7342   H24B 0.7342   C25A 0.7342

H25A

0.7342   H25B 0.7342   C26A 0.7342

H26A

0.7342   H26B 0.7342   C20B 0.1762

H20C 0.1762   H20D 0.1762   C23B 0.2658

71

H23C 0.2658   H23D 0.2658   C24B 0.2658H24C 0.2658   H24D 0.2658   C25B 0.2658H25C 0.2658   H25D 0.2658   C26B 0.2658H26C 0.2658   H26D 0.2658

[(Ph2P(BH3))3Sn]Li(THF) (41)

Table 1 : Crystal data and structure refinement for [(Ph2P(BH3))3Sn]Li(THF)

Identification code kji160027_fa Empirical formula C40H47B3LiOP3Sn Formula weight 794.74 Temperature/K 150.0(2) Crystal system orthorhombic Space group P212121 a/Å 12.0937(3) b/Å 17.3507(5) c/Å 19.0102(6) α/° 90 β/° 90 γ/° 90 Volume/Å3 3988.99(19) Z 4 ρcalcg/cm3 1.323 μ/mm-1 0.791 F(000) 1632.0 Crystal size/mm3 0.2 × 0.16 × 0.11 Radiation MoKα (λ = 0.71073) 2Θ range for data collection/° 5.78 to 52.04

Index ranges -14 ≤ h ≤ 14, -20 ≤ k ≤ 21, -23 ≤ l ≤ 21 Reflections collected 21477 Independent reflections 7674 [Rint = 0.0472, Rsigma = 0.0604] Data/restraints/parameters 7674/71/484 Goodness-of-fit on F2 1.043 Final R indexes [I>=2σ (I)] R1 = 0.0370, wR2 = 0.0655 Final R indexes [all data] R1 = 0.0527, wR2 = 0.0717 Largest diff. peak/hole / e Å-3 0.76/-0.43

72

Flack parameter -0.047(16)

Table 2 Fractional Atomic Coordinates (×104) and Equivalent Isotropic Displacement Parameters (Å2×103) for kji160027_fa. Ueq is defined as 1/3 of of the trace of the orthogonalised UIJ tensor.Atomx y z U(eq)Sn1 5013.0(4) 3701.4(2) 2638.2(2) 21.78(10)P1 7144.7(11) 3695.6(8) 2851.3(8) 27.7(3)P2 4673.7(11) 4894.3(7) 3476.6(7) 23.8(3)P3 5091.5(15) 4519.0(6) 1475.2(6) 24.5(3)C1 7736(4) 3104(3) 2149(3) 27.3(13)C2 8381(5) 3441(3) 1634(3) 35.4(15)C3 8825(5) 3001(3) 1092(3) 41.7(16)C4 8624(5) 2225(3) 1062(3) 40.3(16)C5 7980(6) 1886(3) 1562(4) 46.8(18)C6 7533(5) 2320(3) 2104(3) 38.8(15)C7 7304(5) 3129(3) 3661(3) 32.5(14)C8 6618(5) 2511(3) 3812(3) 35.7(15)C9 6736(6) 2094(3) 4435(3) 43.4(17)C10 7549(6) 2291(4) 4904(4) 47.3(18)C11 8225(6) 2912(4) 4763(4) 51.8(19)C12 8108(5) 3331(3) 4148(4) 42.1(16)C13 5265(4) 4588(3) 4312(3) 24.5(13)C14 5999(4) 5062(3) 4672(3) 28.0(13)C15 6439(5) 4834(3) 5309(3) 34.0(14)C16 6151(5) 4142(3) 5600(3) 35.3(15)C17 5413(5) 3666(3) 5251(3) 33.9(13)C18 4992(6) 3884(2) 4610(2) 30.1(11)C19 3197(4) 4834(3) 3646(3) 23.5(12)C20 2457(5) 4706(3) 3095(3) 30.2(15)C21 1328(5) 4737(3) 3210(3) 31.3(14)C22 913(5) 4892(3) 3862(3) 33.3(14)C23 1628(5) 5016(4) 4410(3) 41.1(16)C24 2762(5) 4988(3) 4305(3) 36.6(14)C25 3609(4) 4610(3) 1329(3) 26.2(13)C26 3108(5) 5324(3) 1401(3) 33.4(14)C27 1976(5) 5404(3) 1331(3) 38.0(15)C28 1333(5) 4771(3) 1203(3) 39.1(15)C29 1813(5) 4059(3) 1132(3) 38.6(15)C30 2945(5) 3973(3) 1187(3) 33.0(14)C31 5591(4) 3898(3) 769(3) 24.2(12)C32 5620(5) 3097(3) 815(3) 30.5(14)C33 6055(5) 2652(3) 282(3) 34.5(14)C34 6462(5) 2999(3) -315(3) 36.4(15)C35 6425(5) 3796(3) -382(3) 32.9(14)

73

C36 5990(5) 4234(3) 155(3) 26.9(13)B1 7920(7) 4673(4) 2900(5) 39(2)B2 4995(8) 5992(3) 3330(3) 30.2(13)B3 5798(7) 5527(4) 1382(4) 35.6(17)Li1 6854(9) 5793(5) 2472(6) 48(3)O1A 8015(16) 6537(12) 2450(20) 39(3)C37A7810(15) 7305(13) 2248(13) 67(5)C38A8888(17) 7669(12) 2116(13) 75(5)C39A9744(14) 7059(10) 2195(17) 62(4)C40A9175(15) 6453(9) 2584(17) 47(3)O1B 7836(16) 6637(11) 2330(20) 39(3)C37B 7620(15) 7296(13) 1922(13) 67(5)C38B 8641(16) 7682(12) 1800(13) 75(5)C39B 9508(14) 7326(10) 2233(16) 62(4)C40B 8947(14) 6685(9) 2599(15) 47(3)

 

Table 3 Anisotropic Displacement Parameters (Å2×103) for kji160027_fa. The Anisotropic displacement factor exponent takes the form: -2π2[h2a*2U11+2hka*b*U12+…].Atom U11 U22 U33 U23 U13 U12

Sn1 16.65(15) 25.15(15) 23.54(17) -1.39(14) -0.4(2) -1.3(2)P1 17.8(7) 26.4(6) 38.7(9) -6.1(7) -3.4(6) -0.1(6)P2 20.4(8) 28.6(6) 22.4(7) -2.3(6) 0.8(6) 0.5(6)P3 22.9(7) 27.6(5) 23.0(6) -0.6(5) 2.1(9) -2.7(8)C1 16(3) 30(3) 35(4) -2(2) -5(3) 3(2)C2 28(3) 32(3) 46(4) -2(3) 0(3) -2(3)C3 36(4) 47(4) 43(4) -3(3) 10(3) 0(3)C4 33(4) 43(3) 45(4) -13(3) 5(3) 3(3)C5 51(4) 30(3) 60(5) -12(3) 3(4) 3(3)C6 40(4) 32(3) 45(4) -4(3) 11(3) -4(3)C7 26(3) 36(3) 35(4) -11(3) -8(3) 10(3)C8 38(4) 31(3) 38(4) -2(3) -5(3) 7(3)C9 50(4) 37(3) 43(4) -3(3) 0(4) 16(3)C10 54(5) 47(4) 41(4) -3(4) -5(4) 26(4)C11 52(5) 66(5) 37(4) -13(4) -20(4) 21(4)C12 35(4) 42(3) 49(4) -11(3) -10(3) 9(3)C13 21(3) 27(2) 25(3) -4(2) 1(2) 0(2)C14 21(3) 33(3) 29(3) -3(3) 0(3) -5(3)C15 25(3) 49(3) 28(3) -5(3) -5(3) -2(3)C16 30(3) 46(3) 30(4) 3(3) -4(3) 3(3)C17 35(3) 34(3) 33(3) 0(3) -2(3) 5(3)C18 28(3) 31(2) 32(3) -5(2) 5(4) -5(4)C19 19(3) 28(3) 24(3) -3(2) 2(3) -1(2)C20 27(3) 39(3) 24(4) 0(3) 3(3) 5(3)

74

C21 24(3) 40(3) 30(3) -8(3) -5(3) 1(3)C22 15(3) 46(3) 38(4) -3(3) 2(3) 3(3)C23 32(4) 67(4) 25(3) -2(3) 7(3) 8(3)C24 24(3) 62(4) 24(3) -4(3) -2(3) 3(3)C25 24(3) 35(3) 19(3) 5(2) 5(2) -3(2)C26 33(4) 35(3) 32(3) 8(3) -2(3) 4(3)C27 35(4) 41(3) 38(4) 9(3) 2(3) 15(3)C28 23(3) 59(4) 35(4) 7(3) -1(3) 7(3)C29 23(3) 49(4) 44(4) -6(3) -3(3) -3(3)C30 29(3) 37(3) 32(3) -3(3) -5(3) 3(3)C31 20(3) 35(3) 18(3) 1(2) -2(2) 0(2)C32 30(3) 34(3) 27(3) 3(3) 3(3) -3(3)C33 43(4) 28(3) 33(4) 0(3) 2(3) -2(3)C34 34(4) 45(3) 31(3) -11(3) 4(3) 1(3)C35 33(3) 43(3) 23(3) 2(3) 5(3) -10(3)C36 24(3) 27(3) 30(3) -1(3) -4(3) 2(2)B1 26(4) 30(3) 62(6) -12(4) -6(4) -6(3)B2 32(3) 26(2) 33(3) -3(2) 4(5) 1(4)B3 42(4) 30(3) 35(4) -3(3) 8(4) -16(3)Li1 35(6) 37(5) 72(9) -4(5) 15(6) -8(4)O1A 27(5) 33(4) 58(10) 5(4) -3(5) 0(4)C37A50(6) 42(4) 110(16) 10(9) -22(7) 11(4)C38A66(8) 47(4) 113(14) 31(8) -22(8) -6(5)C39A43(6) 62(9) 80(6) 19(9) -15(6) -10(5)C40A32(6) 41(8) 69(5) 10(7) -17(6) -4(5)O1B 27(5) 33(4) 58(10) 5(4) -3(5) 0(4)C37B 50(6) 42(4) 110(16) 10(9) -22(7) 11(4)C38B 66(8) 47(4) 113(14) 31(8) -22(8) -6(5)C39B 43(6) 62(9) 80(6) 19(9) -15(6) -10(5)C40B 32(6) 41(8) 69(5) 10(7) -17(6) -4(5)

 

Table 4 Bond Lengths for kji160027_fa.Atom Atom Length/Å   Atom Atom Length/ÅSn1 P1 2.6097(14)   C20 C21 1.384(8)Sn1 P2 2.6444(13)   C21 C22 1.365(8)Sn1 P3 2.6288(13)   C22 C23 1.372(8)P1 C1 1.830(6)   C23 C24 1.387(8)P1 C7 1.836(6)   C25 C26 1.387(8)P1 B1 1.940(7)   C25 C30 1.392(7)P2 C13 1.821(5)   C26 C27 1.382(8)P2 C19 1.818(5)   C27 C28 1.368(8)P2 B2 1.963(5)   C28 C29 1.371(8)P3 C25 1.821(6)   C29 C30 1.380(8)

75

P3 C31 1.825(5)   C31 C32 1.393(7)P3 B3 1.954(6)   C31 C36 1.391(7)C1 C2 1.381(8)   C32 C33 1.377(8)C1 C6 1.384(7)   C33 C34 1.376(8)C2 C3 1.391(8)   C34 C35 1.389(7)C3 C4 1.369(8)   C35 C36 1.376(8)C4 C5 1.363(9)   B1 Li1 2.470(13)C5 C6 1.386(8)   B2 Li1 2.798(14)C7 C8 1.386(8)   B3 Li1 2.477(14)C7 C12 1.388(8)   Li1 O1A 1.908(15)C8 C9 1.394(8)   Li1 O1B 1.904(15)C9 C10 1.371(9)   O1A C37A1.408(16)C10 C11 1.380(10)   O1A C40A1.433(14)C11 C12 1.384(9)   C37A C38A1.470(16)C13 C14 1.390(7)   C38A C39A1.488(19)C13 C18 1.386(6)   C39A C40A1.459(15)C14 C15 1.382(8)   O1B C37B 1.409(14)C15 C16 1.367(8)   O1B C40B 1.438(15)C16 C17 1.385(8)   C37B C38B 1.424(16)C17 C18 1.375(7)   C38B C39B 1.469(18)C19 C20 1.394(8)   C39B C40B 1.477(15)C19 C24 1.385(7)        

 

Table 5 Bond Angles for kji160027_fa.Atom Atom Atom Angle/˚   Atom Atom Atom Angle/˚P1 Sn1 P2 93.60(4)   C21 C20 C19 120.5(5)P1 Sn1 P3 95.56(5)   C22 C21 C20 120.9(6)P3 Sn1 P2 95.17(4)   C21 C22 C23 119.3(5)C1 P1 Sn1 105.94(18)   C22 C23 C24 120.5(5)C1 P1 C7 105.7(2)   C19 C24 C23 120.9(6)C1 P1 B1 109.6(3)   C26 C25 P3 119.5(4)C7 P1 Sn1 103.6(2)   C26 C25 C30 118.4(5)C7 P1 B1 112.2(3)   C30 C25 P3 122.0(4)B1 P1 Sn1 118.8(2)   C27 C26 C25 120.8(6)C13 P2 Sn1 103.66(15)   C28 C27 C26 120.0(6)C13 P2 B2 109.2(3)   C27 C28 C29 120.0(6)C19 P2 Sn1 102.33(17)   C28 C29 C30 120.7(6)C19 P2 C13 102.4(2)   C29 C30 C25 120.1(5)C19 P2 B2 106.0(3)   C32 C31 P3 123.4(4)B2 P2 Sn1 130.0(2)   C36 C31 P3 119.0(4)C25 P3 Sn1 98.04(17)   C36 C31 C32 117.6(5)C25 P3 C31 105.3(2)   C33 C32 C31 121.4(5)C25 P3 B3 109.8(3)   C34 C33 C32 119.9(5)

76

C31 P3 Sn1 108.19(16)   C33 C34 C35 119.9(5)C31 P3 B3 108.5(3)   C36 C35 C34 119.7(5)B3 P3 Sn1 125.1(2)   C35 C36 C31 121.5(5)C2 C1 P1 120.0(4)   P1 B1 Li1 114.8(4)C2 C1 C6 118.2(5)   P2 B2 Li1 97.0(3)C6 C1 P1 121.8(4)   P3 B3 Li1 108.4(4)C1 C2 C3 120.7(5)   B1 Li1 B2 108.9(5)C4 C3 C2 120.1(6)   B1 Li1 B3 113.4(5)C5 C4 C3 119.8(6)   B3 Li1 B2 95.5(4)C4 C5 C6 120.4(5)   O1A Li1 B1 99.0(8)C1 C6 C5 120.7(6)   O1A Li1 B2 121.5(13)C8 C7 P1 121.7(5)   O1A Li1 B3 119.0(12)C8 C7 C12 118.5(6)   O1B Li1 B1 109.0(8)C12 C7 P1 119.8(5)   O1B Li1 B2 119.1(12)C7 C8 C9 121.0(6)   O1B Li1 B3 110.4(11)C10 C9 C8 119.8(6)   C37A O1A Li1 121.1(13)C9 C10 C11 119.5(7)   C37A O1A C40A108.5(9)C10 C11 C12 120.9(6)   C40A O1A Li1 130.3(14)C11 C12 C7 120.2(6)   O1A C37AC38A107.3(11)C14 C13 P2 120.5(4)   C37A C38AC39A107.1(11)C18 C13 P2 121.3(4)   C40A C39AC38A103.6(11)C18 C13 C14 118.2(5)   O1A C40AC39A107.2(10)C15 C14 C13 120.6(5)   C37B O1B Li1 125.9(14)C16 C15 C14 120.5(5)   C37B O1B C40B 108.7(9)C15 C16 C17 119.7(6)   C40B O1B Li1 125.4(12)C18 C17 C16 119.9(5)   O1B C37B C38B 108.2(10)C17 C18 C13 121.1(5)   C37B C38B C39B 109.2(10)C20 C19 P2 120.4(4)   C38B C39B C40B 104.7(10)C24 C19 P2 121.4(4)   O1B C40B C39B 107.9(10)C24 C19 C20 117.8(5)          

 

Table 6 Torsion Angles for kji160027_fa.A B C D Angle/˚   A B C D Angle/˚Sn1 P1 C1 C2 111.8(4)   C19 P2 C13 C18 55.8(5)Sn1 P1 C1 C6 -66.5(5)   C19 C20 C21 C22 0.0(9)Sn1 P1 C7 C8 34.6(5)   C20 C19 C24 C23 -0.1(9)Sn1 P1 C7 C12-143.5(4)   C20 C21 C22 C23 -0.3(9)Sn1 P2 C13 C14130.2(4)   C21 C22 C23 C24 0.3(9)Sn1 P2 C13 C18-50.4(5)   C22 C23 C24 C19 -0.1(10)Sn1 P2 C19 C20-46.0(4)   C24 C19 C20 C21 0.2(8)Sn1 P2 C19 C24140.6(4)   C25 P3 C31 C32 -88.2(5)Sn1 P3 C25 C26111.4(4)   C25 P3 C31 C36 93.3(4)Sn1 P3 C25 C30-64.6(5)   C25 C26 C27 C28 1.4(9)

77

Sn1 P3 C31 C3215.8(5)   C26 C25 C30 C29 -1.0(8)Sn1 P3 C31 C36-162.7(4)   C26 C27 C28 C29 -1.2(9)P1 C1 C2 C3 -179.2(5)   C27 C28 C29 C30 -0.1(9)P1 C1 C6 C5 179.3(5)   C28 C29 C30 C25 1.2(9)P1 C7 C8 C9 -178.8(4)   C30 C25 C26 C27 -0.3(9)P1 C7 C12 C11179.3(5)   C31 P3 C25 C26 -137.2(5)P2 C13 C14 C15179.3(4)   C31 P3 C25 C30 46.8(5)P2 C13 C18 C17-177.9(4)   C31 C32 C33 C34 -0.6(9)P2 C19 C20 C21-173.5(4)   C32 C31 C36 C35 -1.6(8)P2 C19 C24 C23173.4(5)   C32 C33 C34 C35 -0.6(9)P3 C25 C26 C27-176.5(5)   C33 C34 C35 C36 0.7(9)P3 C25 C30 C29175.1(5)   C34 C35 C36 C31 0.5(9)P3 C31 C32 C33-176.8(5)   C36 C31 C32 C33 1.7(8)P3 C31 C36 C35176.9(4)   B1 P1 C1 C2 -17.5(6)C1 P1 C7 C8 -76.6(5)   B1 P1 C1 C6 164.2(5)C1 P1 C7 C12105.4(5)   B1 P1 C7 C8 164.0(5)C1 C2 C3 C4 0.1(10)   B1 P1 C7 C12 -14.1(6)C2 C1 C6 C5 1.0(9)   B2 P2 C13 C14 -11.5(5)C2 C3 C4 C5 0.5(10)   B2 P2 C13 C18 167.9(5)C3 C4 C5 C6 -0.3(10)   B2 P2 C19 C20 92.3(5)C4 C5 C6 C1 -0.4(10)   B2 P2 C19 C24 -81.1(5)C6 C1 C2 C3 -0.8(9)   B3 P3 C25 C26 -20.6(6)C7 P1 C1 C2 -138.7(5)   B3 P3 C25 C30 163.4(5)C7 P1 C1 C6 43.0(6)   B3 P3 C31 C32 154.2(5)C7 C8 C9 C10-0.7(9)   B3 P3 C31 C36 -24.3(5)C8 C7 C12 C111.1(9)   Li1 O1A C37AC38A-166(2)C8 C9 C10 C111.7(9)   Li1 O1A C40AC39A154(3)C9 C10 C11 C12-1.3(10)   Li1 O1B C37B C38B -165(3)C10 C11 C12 C7 -0.1(10)   Li1 O1B C40B C39B 166(3)C12 C7 C8 C9 -0.7(8)   O1A C37A C38AC39A4(3)C13 P2 C19 C20-153.2(4)   C37A O1A C40AC39A-24(3)C13 P2 C19 C2433.4(5)   C37A C38A C39AC40A-18(3)C13 C14 C15 C16-0.7(9)   C38A C39A C40AO1A 25(3)C14 C13 C18 C171.5(8)   C40A O1A C37AC38A12(3)C14 C15 C16 C170.1(9)   O1B C37B C38B C39B -9(3)C15 C16 C17 C181.3(9)   C37B O1B C40B C39B -11(3)C16 C17 C18 C13-2.1(9)   C37B C38B C39B C40B 2(3)C18 C13 C14 C15-0.1(8)   C38B C39B C40B O1B 5(3)C19 P2 C13 C14-123.6(4)   C40B O1B C37B C38B 12(3)

 

Table 7 Hydrogen Atom Coordinates (Å×104) and Isotropic Displacement Parameters (Å2×103) for kji160027_fa.Atom x y z U(eq)

78

H2 8523 3979 1651 42H3 9268 3240 741 50H4 8932 1925 693 48H5 7838 1348 1540 56H6 7082 2078 2448 47H8 6058 2369 3486 43H9 6254 1676 4533 52H10 7647 2001 5323 57H11 8779 3055 5092 62H12 8579 3758 4059 50H14 6200 5547 4477 34H15 6946 5161 5548 41H16 6455 3988 6038 42H17 5198 3189 5455 41H18 4505 3547 4367 36H20 2731 4598 2637 36H21 835 4649 2829 38H22 137 4914 3935 40H23 1344 5122 4866 49H24 3247 5076 4689 44H26 3548 5765 1501 40H27 1645 5899 1372 46H28 553 4824 1164 47H29 1363 3621 1044 46H30 3270 3479 1127 40H32 5334 2852 1223 37H33 6073 2107 327 41H34 6769 2694 -681 44H35 6698 4037 -795 39H36 5962 4778 105 32H1A 7780(50) 4920(30) 2330(40) 59H1B 7460(60) 5010(40) 3270(40) 59H1C 8760(60) 4600(30) 3010(40) 59H2A 4690(50) 6270(30) 3820(30) 45H2B 4500(50) 6170(30) 2910(30) 45H2C 5910(50) 6060(30) 3250(30) 45H3A 6690(60) 5410(40) 1410(40) 53H3B 5510(50) 5760(30) 870(30) 53H3C 5520(50) 5880(30) 1840(30) 53H37A7413 7581 2628 80H37B 7350 7319 1817 80H38A9019 8089 2459 90H38B 8911 7889 1636 90H39A9994 6871 1730 74H39B 10391 7253 2460 74

79

H40A9434 5940 2427 57H40B 9324 6504 3094 57H37C 7102 7642 2173 80H37D7280 7145 1470 80H38C 8568 8235 1921 90H38D8842 7644 1296 90H39C 9810 7701 2575 74H39D10119 7132 1936 74H40C 9344 6195 2511 57H40D8936 6780 3112 57

 

Table 8 Atomic Occupancy for kji160027_fa.AtomOccupancy   AtomOccupancy   AtomOccupancyO1A 0.4909   C37A 0.4909   H37A 0.4909H37B 0.4909   C38A 0.4909   H38A 0.4909H38B 0.4909   C39A 0.4909   H39A 0.4909H39B 0.4909   C40A 0.4909   H40A 0.4909H40B 0.4909   O1B 0.5091   C37B 0.5091H37C 0.5091   H37D 0.5091   C38B 0.5091H38C 0.5091   H38D 0.5091   C39B 0.5091H39C 0.5091   H39D 0.5091   C40B 0.5091H40C 0.5091   H40D 0.5091    

80