1

Al-Mustansiriya J. college of education vol (5)_pp 1-14

14- 0( 2102العدد الخامس ) –مجلة كلية التربية الجامعة المستنصرية

Synthesis and characterization of mixed ligand complexes of some metals with

( L- phenylalanine and nicotinamide) T.H Al-Noor S. M H. OBED S.S.Abd-Al-Razzaq

Chemistry Department.Ibn-AI-Haithem College of Education,

University of Baghdad-IRAQ

2

Synthesis and characterization of mixed ligand complexes of some metals with

( L- phenylalanine and nicotinamide) T.H Al-Noor S. M H. OBED S.S.Abd-Al-Razzaq

Chemistry Department.Ibn-AI-Haithem College of Education,

University of Baghdad-IRAQ

Abstract :

This paper presents the synthesis and study of some new mixed-liagnd complexes

containing nicotinamide(C6H7N2O) symbolized (NA) and phenylalanine

(C9H11NO2)symbolized (pheH)] with some metal ions.

The resulting products were found to be solid crystalline complexes which have

been characterized by :Melting points, Solubility, Molar conductivity.

determination the percentage of the metal in the complexes by flame(AAS),

magnetic susceptipibility, Spectroscopic Method [FT-IR and UV-Vis].

The proposed structure of the complexes using program , chem office 3D(2006) .

The general formula have been given for the prepared complexes :[M(NA)2(phe)]cl

M(II): Mn(II) ,Co(II) , Ni(II) , Cu(II) , Zn(II) , Cd(II) & Hg(II) .

NA = Nicotinamide= C6H7N2O

Phe - = phenylalanine ion = C9H10NO2

-

The results showed that the deprotonated ligand (phenylalanine acid) to

(phenylalanilate ion (Phe -) by using (NaOH) coordinated to metal ions as bidentate

ligand through the oxygen atom of the carboxylate group (COO), and the nitrogen

atom of the amine group (NH2). The nicotinamide coordinated as a monodendato

through the nitrogen of the pyridine group.

3

ةلفلزياكاندمن )الفنيل االنين والنيكوتين امايد( مع بعض أيونات العناصر يتحضير وتشخيص معقدات مختلطة الل ساهرة صادق عبد الرزاق شذى محمد حسن عبيد تغريد هاشم النور

جامعة بغداد / كلية التربية ـ ابن الهيثم / قسم الكيمياء

: الخالصة مختصره تضمن البحث تحضير وتشخيص معقدات ذات ليكاندات مختلطة من حامض الفنيل أالنين و

(pheH) والنيكوتين أمايد (C6H7N2O) ( ومختصره(NA مع بعض أيونات العناصر الفلزية و المعقدات

المحضرة بلورات صلبة درست من النواحي اآلتية:

درجااات االنصااهارت التوصاايلية الكهرباميااة الموالريااةت الاوبانيااةت الخااوات المغنانيساايةتتقدير النساابة الم ويااة

قدات بوسانة مطيافية االمتصات الاريت الدراسات الطيفية: وتضمنت أنياا)) اشعاعة لأليون الفلزي في المع

Chem. Office– Cs. chem– 3D)نامج ت مع استعمال البرالمرمية –تحت الحمراءت اشععة فوق البنفسجية

pro 2006) .في رسم أعكال المعقدات

ت المحضرة :ومن هاه المعطيات أمكن إعطاء الصيغة العامة اآلتية للمعقدا

[M(NA)2(phe)] cl M(II): Mn(II) ,Co(II) , Ni(II) , Cu(II) , Zn(II) , Cd(II) & Hg(II) .

NA = nicotinamide= C6H7N2O ,

Phe- = C9H10NO2

-

المعقدات المحضرة بلورات صلبة بعضها ملون درست من النواحي اآلتية:

تقاادير النساابة الم ويااة لأليااون الفلاازي فااي الموالريااةت الاوبانيااة تدرجااات االنصااهارت التوصاايلية الكهرباميااة

المعقاادات بوسااانة مطيافيااة االمتصااات الاااريت محتااوت الكلااور باسااتعمال نريقااة مااورت الدراسااات الطيفيااة:

.Chem)ناامج ت ماع اساتعمال البرالمرمياة –وتضمنت أنيا)) اشععة تحت الحماراءت اشعاعة فاوق البنفساجية

Office– Cs– 3D pro 2006) . في رسم أعكال المعقدات

Cl [ [M (C6H6N2O)2 ومن الدراسات التشخيصية اقترحت الصيغة العامة اآلتية لهاه المعقدات

(C9H11NO2)

Phe) لفنيل االنينيتت يسلك الليكاند حامض االنثرانيلك )الفاقد بروتون والمتحول إلى أيون ا-

باستعمال القاعدة (

((NaOH كليكاناااد ئناااامي السااانت إذ يااارتبر بااااشيون المركااازي عااان نريااا ذرة اشوكساااجين فاااي مجموعاااة

الكاربوكسيل وذرة النتروجين في مجموعة

السن إذ يرتبر من خالل ذرة النتروجين في حلقة البيريدين. يمين .بينما النيكوتين أمايد يسلك كليكاند أحادشا

4

Introduction Nicotinamide (NA) is a form of niacin is very prevalent in plants and human tissues a

deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. The

Nicotinamide (3-pyridine carboxamide) is a pyridine derivative which is important bio ligand for

human health. [1]

In the recent decade, the synthesis and structure of new series of bimetallic complexes with A

has been studied by various methods because of biological importance of NA [2]. Although the

synthesis, characterization and electrochemical behavior of complexes of nicotinamide with some

metal ions (Cu(II), Co(II), Ni(II), Pb(II), Cr(III) and Zn(II)) were studied [3−6]

A series of mixed ligand containing nicotinamide and saccharinato complexes [7-9]

Inorganic elements like transition metals are vital to the proper functioning of the body’s

processes. Metal ions have the ability to form strong bonds and be stable in more than one

oxidation state. Iron has a major role in biological reactions. Iron in the blood chelates with

protoporphyrin to form heme, a prosthetic group of proteins such as myoglobin, hemoglobin,

catalase, peroxidase, and cytochrome c. [10] It also plays a role in enzyme activity. Enzymes

called oxygenases catalyze the cleavage or degradation of aromatic amino acid rings in biological

systems. For example the degradation of phenylalanine begins with its hydroxylation to tyrosine, a

reaction catalyzed by phenylalanine hydroxylase. The active site of this enzyme contains iron that

is not part of heme or an iron-sulfur cluster [11]. Zinc is found only in the 2+ state in biological

systems. It is known to form complexes with amino acids such as L-serine, L-aspartic acid, L-

lysine, and L-phenylalanine [10-12].Table (1) shows some properties of tow ligands (nicotinamide

and L-phenylalanine).

Table (1) some properties of (Nicotinamide and L-phenylalanine)

In this paper we present the synthesis and study of metal Complexes contain mixed Ligand of

L-phenylalanine as a primary and Nicotinamide as secondary ligand .

Synonyms

Nicotinamide

3-

yridinecarboxamide

3-Carbamoyl pyridine

L-phenylalanine

Symbol NA Phe

Chemical

structure

NH2

CH CH2C OH

O

Molecular formula C6H7N2O C9H11NO2

Molecular weight 122.12 165.19

m.p 130-1330C 272

0C

Physical state Crystalline powde

Crystalline powder

appearance white white

NO

H2N

5

Experimental:

a-chemicals and instruments: L-phenylalanine acid and Nicotinamide were purchased from

(Merck),solvents and all the metal ions M(II): Mn(II) ,Co(II) , Ni(II) , Cu(II) , Zn(II) , Cd(II) & Hg(II) .were of analar

grade (BDH). They were used in the form of chlorides without further purification.

b- Instruments: FT-I.R spectra were recorded as KBr discs using Fourier transform Infrared

Spectrophotometer Shimadzu 24 FT-I.R 8400s. Electronic spectra of the prepared complexes were

measured in the region (200- 1100) nm for 10-3

M solutions in DMF at 25ºC using shimadzu-U.V-

160 . A Ultra Violet Visible Spectrophotometer with 1.000 ± 0.001 cm matched quartz cell. While

metal contents of the complexes were determined by Atomic Absorption (A.A)Technique using

Japan A.A-67G Shimadzu . Elemental Analysis (C.H.N.) was carried out with: Perkin Elmor B-

240 Elemental Analyzer. Electrical conductivity measurements of the complexes were recorded at

25ºC for 10-3

M solutions of the samples in DMF using pw9527 Digital conductivity meter

(Philips). Magnetic susceptibility measurements were measured using Bruker magnet

BM6.Melting points were recorded by using Stuart melting point apparatus. The proposed

molecular structure of the complexes were determinated by using chem. office prog, 3DX (2006).

B: General synthesis :

1- Nicotineamide solution: dissolve [(0.224 gm) 2m.mol] in ethanol.

2-Sodium phenylalanin (Phe- Na+) was prepared by a naturalization of L-phenylalanine(PheH)

[0. 165 gm (1mmol)] solution with [0.04 gm(1mmol)]of sodium hydroxide solution.

C- General synthesis of complexes:

The complexes were prepared by the addition of ethanolic solutions of the(Na+Phe

-)

and (nicotinamide solution) to warm stirred ethanolic solution of the respective

metal (II) chloride in the stoichiometric ratio metal: ligands (M: Phe:2NA). The

mixture was stirred for one hour at room temperature , crystalline precipitates

observed . The resulting precipitates were filtered off , recrystallized from ethanol

and dried at 50C ْ . according to the following reaction (scheme -1)

scheme (1) Synthesis of the mixed complexes

M

CH

H2N

C

O

O

N

O

H2N

NO

NH2

M(II)= Mn(II) ,Co(II) , Ni(II) , Cu(II) , Zn(II) , Cd(II) & Hg(II)

H2N

O

OHL-phenylalanine

+

NO

H2N

nicotinamid

2 +MCl2

ethanol

Cl

6

Results and Discussion

Physical properties of the prepared complexes: Table (2) shows the physical data for the prepared complexes which show different melting

points, all of them were higher than the two ligands, All the complexes are colored, non-

hygroscopic and thermally stable solids indicating a strong metal-ligand bond. The complexes are

insoluble in water but soluble in common organic solvents such as ethanol, ethyl alcohol,

acetone, chloroform ,DMF and DMSO solvents. The elemental analysis(C.H.N) were found to be

in agreement with calculated values. Table(2) includes the physical properties and elemental

analysis. The analytical data confirmed the (1:2:1)(M:2NA: Na+ Phe -

) composition of the

complexes.

Molar conductance:

The molar conductance values of the complexes in DMF at 10-3

M concentration at 2980K

Table (2) are found to be (52.75-80.68 ) µS.cm-1

, for complexes of composition

[M (phe) (NA)2]Cl indicating their electrolytic nature correspond to 1:1 electrolytes. [12 -13]

Atomic Absorption :

The atomic absorption measurements (Table-2) for all complexes gave approximated values

for theoretical values.

In conclusion, our investigation this suggest that the ligands L-phenylalanin Acid and

Nicotinamide coordinate with M (II) forming tetrahedral geometry (Figur-2) .

The electronic spectra : The electronic spectra of all compounds (Ligands and complexes) are listed in Table (3)

figures(4-6) together with the proposed assignments and suggested geometries.

The spectrum of the free ligand (pheH) in DMF solvent show a high intensity band in wave

length 271.5nm (36832.42 cm-1

) εmax (1574 l.mol-1

.cm-1

) assigned to (n→ π*) and free ligand

(nicotinamide) (NA) shows a high intensity band in wave length 276 nm (3623 cm-1

) max (626

l.mol-1

.cm-1

) assigned to (π - π*) Fig1 [14] in addition to these transitions the spectra of the

complexes exhibited another new bands in the visible region caused by charge transfer (C.T)

assigned to (d-d) transitions between the metal ion and the ligands . [15-16]

[Ni (C12H22N5O5)]Cl (d8) : The green complex spectrum revealed the following absorption bands ,

(3020m-1

attributed to the charge transfer (C.T) , two absorptions at (2074)cm-1

and (12468)cm-1

were due to the electronic transition 3T1(f) 3

T1(P) and 3T1(f) 3

A2(f).

[Cu(C12H22N5O5)]Cl (d9) : The Dark--blue complex of Cu(II) gave band at wave number

(40861)cm-1

caused by (C.T) transition and only one absorption band was observed in the visible

region at (18832) cm-1

which originated to (d-d)electronic transition type [2B1→ 2E1] ,apposition

of this peak is a good agreement with reported for Cu(II) distorted tetrahedral geometry [17]

[Zn(C12H22N5O5)]Cl,[Cd(C12H22N5O5)Cl and [Hg(C12H22N5O5)]Cl: (d10

)(white complexes) : Because

of filled d- shell of these complexes, no ligand field absorptions band was observed, therefore the

bands appeared in the spectra of three complex could be attributed to charge transfer transition. in

fact this result is a good agreement with previous work of tetrahedral geometry [18-19]

The µeff of values for the following high spin tetrahedral complexes were found as

complexes for Co (II) (d7) complex is 4.67 B.M , for Ni(II) (d

8) complex is 4.23 B.M , for Cu (II)

complex is 1.67 B.M .While magnetic susceptibility measurements for Cd(II),Hg(II) and Zn(II)

(d10

)(white complexes) showed diamagnetic as expected from their electronic configuration . [19]

7

Fourier transform infrared spectra : The analysis of the spectra was performed in comparison with ligand (Sodium phenylalanilate

, nicotinamide).The assignment of some of the most characteristic FT-IR band of the complexes

are shown in (Table -4) together with those of (Sodium anthranilate ,and nicotinamide recorded

for comparative purposes and facilitate the spectral analysis .Absorption bands in the (648-

514)cm-1

region are considered to be due to metal-nitrogen vibrations [18,19] whilst those

occurring around (418-460)cm-1

are thought to arise from metal-oxygen vibration .[20-21]and

finally the sharp bands at (3368-3405) asym cm-1,

(3161-3357) sy m are attributed to the N-H2

stretching vibration respectively [22-23].

Nomenclature of prepared complexes : Table (5) Shows empirical formula and nomenclature (IUPAC) with abbreviated .

Proposed molecular structure :

Studying complexes on bases of the above analysis , shows the existence of tetra coordinated

[M(phe) (NA)2] Cl, M(II) = Mn(II) ,Co(II) , Ni(II) , Cu(II) , Zn(II) , Cd(II) & Hg(II) .

A proposed models of the species were built with chem. 3D 3D shows in Figure. ( nnn)

Figure (2) : The proposed structure of the complexes

Complexes Nomenclature Abbreviation

[Mn(C21H22N5O4)] Cl phenylalaninatobisnicotinamidemanganate (II)chloride [Mn(NA)2(phe)] Cl

[Co(C21H22N5O4)] Cl Phenylalaninatobisnicotinamide cobaltate (II) chloride [ Co(NA)2(phe)] Cl

[ Ni(C21H22N5O4)] Cl phenylalaninatobisnicotinamide nickelate (II) chloride [ Ni(NA)2 (phe)] Cl

[Cu(C21H22N5O4) ] Cl phenylalaninatobisnicotinamide cuprate (II) chloride [Cu(NA)2(phe)] Cl

[Zn(C21H22N5O4)] Cl[ phenylalaninatobisnicotinamide zincate (II) chloride [ Zn(NA)2(phe)] Cl

[Cd(C21H22N5O4)] Cl phenylalaninatobisnicotinamidecadmate (II) chloride [Cd(NA)2(phe)] Cl

[Hg(C21H22N5O4)] Cl phenylalaninatobisnicotinamidemercurate (II) chloride [Hg(NA)2(phe)] Cl

M

CH

H2N

C

O

O

N

O

H2N

NO

NH2

M(II)= Mn(II) ,Co(II) , Ni(II) , Cu(II) , Zn(II) , Cd(II) & Hg(II)

Cl

8

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Technol. 41, No. 3, 314 – 320 (2006).

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339-347,Dec.(2002).

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5- S. Çakır and I. Bulut, J. Electroanal. Chem. 518, 5 (2002)

6- S. Cakir, I. Bulut, and K. Aoki, J. Chem. Cryst. 33, 875 (2003).

7- Quinzani, O.V., Tarulli. S.Piro.O.E., Baran. E.J. Casteliano.E.E, Naturoforsch. Z,

52b, 183 (1997) .

8- Quinzani.O.V, Tarulli.S, marcos. C,Garca. S-Grand a, E.J Baran, Z.Anorg. Allg.

Chem.625,1848 (1999) .

9- Baran.E.J, wanzer . C.C, Rossi. M, caruso. Z, Anorg.Ally.chem. 626,701 (2000)

10-Harvey, David. In Spectroscopic Methods of Analysis In Modern

Analytical Chemistry,; McGraw Hill Companies, Inc.: Boston,; 406(2002).

11-Krishna, Thatavarthy Rama; Jayaraman, Narayanaswamy. . J. Chem. Soc., Perkin

Trans., 1, 746-754(2002).

12- Gleeson, B. Claffey, J. Hogan M., Müller- Bunz H., Wallis D., Tacke M., J.

Organomet.Chem. 694, 1369–1374 (2009).

13- 12- Geary , W.J, Coord. Chem. Rev, 7819(1971).

14- M.R. Ermarcora; D.W .Ledman; R.O.Fox. Nat. struct. Biol. , 3 , p. 59 (1996)

15- S.Cakir , E.Bicer , H. Icbudak , P.Naumov, H.Korkmaz and O.Cakir . J.Che, 75, p.

371-377 (2001) .

16. C.Preti and G. Tosi , J.Inorg.Nucl. chem, 36, p. 3725 (1974) .

17. A.B.P, Lever, “Inorganic electronic spectroscopy” New York 2nd (1984).

18- A. S, Shihri, Petrochemical Acta part A60,1189-1192 (2004).

19- Singh P.D. , Jha N.K. and Mishra L. K., J. Inorg. Nucl. Chem. 42 (2):282 (1980).

20- Shriver & Atkins, Freeman, “ Inorganic Chemistry”, 3 nd ., Elsevier publishing

company , London , (1999).

21.N.Sarikavakli,and G.Irez, Turk., J. Chem.Sos 29,107, (2005).

22. Nishida. Y., Niinuma. A., Abe. K., Inorg. Chem. Commun. 12 198–200(2009)

23. Nakamoto; K“ Infrared spectra of Inorganic and coordination compounds “4ED th ;

J. Wiely and Sons, New York, (1996) .

9

Table 2. Analytical data and some physical properties of the complexes.

m = Molar Conductivity , M.p= Melting points

Compounds

M.p

(de) °c

Color

m

µS.cm-1

& Metal % (C.H.N)

C H N Metal %

Nicotinamide

NA 272 White

- - - -

phenylalanine 291

White 2.8

- - - -

[Mn(C21H22N5O4) ] Cl >350

Dark-

brown

52.75 52.42

(51.88)

4.17

(3.88)

16.09

(16.00)

12.62

(11.96)

[Co(C21H22N5O4) ] Cl 277 Pale-brown 57.54

51.95

(50.16)

4.13

(4.12)

15.94

(15.30)

13.41

(12.86)

[ Ni(C21H22N5O4) ] Cl 311 green

70.67 51.97

(52.96)

4.13

(4.12)

15.95

(16.11)

13.37

(14.12)

[Cu(C21H22N5O4) ] Cl 251 Dark--blue 69.37 51.41

(50.30)

4.09

(4.12)

15.78

(15.90)

14.31

(14.99)

[Zn(C21H22N5O4) ] Cl[ 271 White 65.24

51.19

(50.82)

4.07

(4.86)

15.71

(15.86)

14.67

(14.90)

[Cd (C21H22N5O4) ] Cl 139 White 70.42

46.36

(45.60)

3.68

(2.66)

14.21

(13.24)

22.81

(21.66)

[Hg(C21H22N5O4) ] Cl 281 White

64.56 39.28

(39.20)

3.12

(2.86)

12.05

(12.00)

34.53

(---)

11

Table (3). Electronic Spectra of the tow ligands and there complexes

Probable

figure

µ eff

(B.M)

Assignment (cm-1

) λ ( nm) Compound

- *

*

35714.28

3623.88

281

276

(NA)

- n → π* 36832 271 C9H11NO2

tetrahedral

Ligand field

14

)(1

4A

P

T

3464

17825 291

561 [Mn(C21H22N5O4) ]

Cl

tetrahedral 4.67 Ligand field

)(1

4

)(2

4

P

T

f

A

34113

27777

294

361 [Co(C21H22N5O4) ] Cl

tetrahedral

4.23

C.T

C.T

34364.26

43478

231

291

[ Ni(C21H22N5O4) ] Cl

distorted

tetrahedral

1.67 C.T

2B1→ 2E1

41841

18832 239

531

[Cu(C21H22N5O4) ] Cl

tetrahedral diam C.T

C.T

35587.18

31645.56

281

316

[Zn(C21H22N5O4) ] Cl

tetrahedral diam C.T

32258 311 Cd(C21H22N5O4) ] Cl

tetrahedral diam C.T

36911 272 Hg(C21H22N5O4) ] Cl

11

Table (3) FT-IR spectral data of the Ligands and there complexes

Sym: symmetric, asy: asymmetric, am: amide, py: pyridine, o.p: out of plane, str: stretching, v.s: very strong,

s: strong, m: medium, w: week, sh: shoulder.

M-O M-N

(-coo-)

asym sym O=CN Bend(am)

i.p(CH) (py)

C=N

Str (am) (C-C) str

(py) ring str

(py) NH2(def)

(am) C=O

str(amid) NH2sym

str NH2asy

str Compound

_ _ _ _ 736vs 1230vw 1090vw

5931 vs 1423vs 1123m

1592vs 1618vs 1679vs 1697sh

3161s 3368vs Nicotinamide(NA

)

_ _ 1300s

1560 vs _ _ _ _ _ _ 3350s 3519s

C9H11NO2

491m

514 m 1406vw 1584vw 057 _ 1385 1436m 1598m 1628m 1678m 3355w 3348 s [Mn(na)2(phe)] Cl

480w 516m 1407vs 1537vs 752vs 1260

1039m 1320m

1458s 1190w

vs5135

1614vs 5707

m 3299s 3307vs [Co(na)2(phe)] Cl

414m 514s 1406vs 1541vs 754s 1240w 1051m

1326m 1458s 1199w

vs5135

1616vs 5700

m 3298s 3355s [Ni(na)2(phe)] Cl

480m 557m 1444vs 1542vs 752s 1240w 1000w

1383m 1406s 1199w

vs5153

1623vs m5775 3319m 3332m [Cu(na)2(phe)] Cl

470m 557m 1406vs 1541vs 756vs 1242m 1095m

1326m 1483w vs5139

1614vs m5707 3313m 3332m [Zn(na)2(phe)]Cl

480 560m 14030s 1604s 756vs 1232m 1023m

1379m 1430w vs5771

1622vs m5797 3058s 3337s [Cd(na)2(phe)] Cl

424 562m 1400vs 1537vs 756vs 1166w 1081m

1354s 1488s 1166w

vs5153

1618vs m5797 3058s 3307s [Hg (na)2(phe)] Cl

12

Figure. (1)The (UV-Vis) Spectra of C6H6N2O

4

Figur.(1)The (UV-Vis) Spectrum of C6H6N2O

Figur.(2)The (UV-Vis) Spectrum of C7H7NO2

13

Figure.(4) FT- IR spectrum of C6H6N2O

Figure (5) FT-IR spectrum of Phanylalanin

14

Figure.( 5) FT- IR spectrum of (C7H7NO2)

Figure. (6) FT- IR spectrum of (C19H18MnN5O4)