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The Synthesis of FourNew Bis(Amino-p-Chlorophenylglyoximes) andtheir Polymeric ComplexesAli Ihsan Pekacar a , Bedrettin Mercimek b & EmineÖzcan ca Niğde University, Faculty of Arts and Sciences,Chemistry Department, 51200, Niğde, Turkeyb Selçuk University, Faculty of Arts and Sciences,Chemistry Department, 42079, Konya, Turkeyc Pamukkale University, Faculty of Arts and Sciences,Chemistry Department, Denizli, TurkeyVersion of record first published: 18 Aug 2006.

To cite this article: Ali Ihsan Pekacar , Bedrettin Mercimek & Emine Özcan (1997):The Synthesis of Four New Bis(Amino-p-Chlorophenylglyoximes) and their PolymericComplexes, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 27:3,455-463

To link to this article: http://dx.doi.org/10.1080/00945719708000201

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SYNTH. REACT. INORG. MET.-ORG. CHEM., 27(3), 455-463 (1997)

THE SYNTHESIS OF FOUR NEW

AND 1HEIR POLYMERIC COMPLEXES BIS(AMIN0-p-CHL OROPHENYL GL YOXMES)

Ali hsan Pekacar* Nigde TJniversity, Faculty of A r t s and Sciences,

Chemisty Department, 51200 Nigde, Turkey

Bedrettin Mercimek Selguk University, Faculty of A r t s and Sciences, Chemistly Department, 42079 Konya, Turkey

Pamukkale Univergity, Faculty of Arts and Sciences, Chemistry Department, Denizli, Turkey

Emine Ozcan

ABSTRACT

In thiv study, four new bis(amino-p-chlorophenylglyoximes),

1,2-phenylenebis(aminomino-pchlorophenylglyoxime) L1€i2, 1,5-naphthylenebis(amino-p

chlorophenylglyoxime) L2H2, 3,4-tolylenebi~(amino-p-chlorophenylglyoxime) L3H7,

and 2,6-pyridylbis(amino-pchlorophlenylglyoxime) L4H2, have been synthesized from

&-p-chlorophenylchloroglyoxime and the corresponding aromatic diamines. Their

polymeric complexes with Ni(lI), Co(n) and Cu(II) have been prepercd. The Ni(I1) and

Cu(II) complexes of these ligands have been found to be square-planar, while the Co(i1)

complexes are octahedral with water molecules as axial ligands. 111 NMR, AAS, IR,

magnetic susceptibility and elemental analytical data of the complexes and ligands are

discussed.

455

Copyright 0 1997 by Marcel Dekker, Inc

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456 PEKACAR, MERCIMEK, AND OZCAN

INTRODUCTION

Since the increasing we of coordination compounds in analytical, pigment,

medicinal and biochemistry, many investigators have studied these topics, especially the

important role of the complexes of 1,Zdioximes in coordination chemistry. The

transition metal complexes of v*dioximes have been of particular interest as far as

biological model compounds1-3 are concerned. Thus, the synthesis of substituted

aminoglyoximes from a&-chloroglyoxime or a&-chlorophenylchloroglyoxime and the

corresponding amines has been reported*-’. It has been found that in these compounds

the two oxime groups are not equivalent. Additional substituents on the aromatic group,

bound to the N-atom of aminoglyoxime, are expected to enhance the difference between

the two oxime groups. In this paper we report the synthesis of polymeric complexes of

four new bis(amino-pchlorophenylglyoximes) as examples of unsymmetrically

substituted 1,3-dioximes.

RESUL TS AND DISCCTSSION

In this study, four new bis(amino-gchloroglyoximes) were synthesized from the

reaction of a&-pchlorophenylchloroglyoxime and the corresponding aromatic diamines

in ethanol at -10oC. The general structures of these compounds are given in Fig. 1. The

structures of the new ligands were confirmed by elemental analyses, lH NMR and IK

spectral data shown in Tables I, I1 and 111, respectively.

~ H N M R Svec:ra ofLipMdF and Comvkes

In the 1H NMR spectra of the ligands, two peaks are present for the OH protons of

the oxime groups. When the chemical shifi values of the two OH protons are compared

in the four different ligmds, the ones at lower field resemble each other quite closely

(12.07-11.61 ppm), however,for those at the higher field (11.17-10.30 ppm) a

considerable difference is observed (Table 11). The chemical shift for OH protons

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bis(AM1NO-p-CHLOROPHENYLGLYOXIME) COMPLEXES 457

Fig. 1. General Formulae of Ligands

TabkI. The Colors, Yields, Melting Points and Elemental Analytical Regultg of the Ligands.

aDisappears on D,O exchange 6: singlet m: mukiplet

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458 PEKACAR, MERCIMEK, AND OZCAN

Tabklll. Characteristic JR Bands of the Ligands as KRr Pellets (cm-I)

have characteristic value for these types of oximes8-10. The two deuterium

exchangeable singlets correspond to two non-equivalent OH protons which also indicate

the a-configuration of the OH group relative to each other1>5p8-12. The deuterium

exchangeable NH protons, neighboring the oxime groups, and the aromatic C-H protons

were observed at 8.63-8.52 ppm and 8.15-6.76 ppm, r e ~ p e c t i v e l y ~ ~ ~ ~ ~ ~ ~ ~ - ~ ~ . The

chemical shift values of the methylene protons appeared at 2.39 ppm as singlets.

a

Due to the low solubilities of the complexes in organic solvents, 113 NMR spectra

could not be obtained. The metal-ligand ratios in all these polymeric complexes were

1:1, but the Co(II) complexes had two coordinated water molecules for each complex.

Consequently, an octahedral structure for the Co(1I) and a square-planar structure for the

Ni(1I) and Cu(I1) compounds are proposed4 , Fig. 2.

IR Spectra ofLipandS and Comvlolc

In the IR spectra of the ligands (Table 110, NH (3460-3420 an-'), OH (3320-

3280 cm-'), C=N (1640-1620 cm-l), C-C1 (700-690 cm-l) and NO (1010-940 cm-1)

&etches appear at frequencies expected for substituted bis(amino-pchlorophenyl-

glyoximes)8-11,14,15.

In the JR spectra in Table I1 and lV of the complexes, the shifts of the C-N

stretching frequency to a lower frequency and the vibration of the N-0 band to a higher

frequency indicated the formation of coordination bonds between metal and the nitrogen

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bis(AMIN0-p-CHLOROPHENYLGLYOXIME) COMPLEXES 459

n MCI2

n Q C-C /iv"" H

// \ I N-R-N

I \ /;"""-a HON

H C-C

H*/ Q CI

- n

M = Ni(II), Cu(II), Co(II).ZHfl

Fig. 2. Octahedral andsquare-planar Pobmeric Metal ComprpXes

of B i s ( M c i n o - p c h l o r o p h e ~ ~ ~ ~ ~ ) .

I*&& f K Tht Colors, Mclting Pointsa, Yicfck and Elemental Analytical Results of the Complexes.

Cotnpounb --__

f=u

558.00

562.86

594.28

608 06

612.92

644.34

__

____ 512.03

576.89

608.30

___

-~

558.99

563.85

595 26

.-

~ ..~

Brown

Red

47.88

Bmm

und)% ___ - N M

15.06 10.52 (15.W) i10.67) 14.93 11 29

14.14 9.91 (14.17) (9.71)

13.82 965 j 1 3 . 7 4 (963)

13.71 10.36 (13.52) (10.30) 13.04 9.14

(13.34) (9.21)

14.69 10.26 (1457) (10.37)

14.56 11 01 (1437)- (10.87)

13.81 969 (13.61) (9.55)

17.54 10.50 117.35) (10.61)

17.39 11.27 (17.01) (11.?8) 16.41 9.90

(16.32) (9.98)

(11.4cj

_-

____

~

a Melting points of dl compounds are above 360 OC.

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460 PEKACAR, MERCIMEK, AND OZCAN

atoms of the liganh. In the case of the Co(II) complexes, the coordinated H2O groups

are identified by a broad OH absorption at around 3540-3300 cm-l which keeps its

intensity even after heating at 1 10°C for 24 h.

Magnetic Susceptility ofNit1I). CutII) and Co{II) Coinvhes

The magnetic susceptibility values of the complexes (Table V) show that the ds

configuration of the Ni(II) complexec ic diamagnetic, while the d9 Cu(I1) complexen and

d7 Co(I1) complexes are paramagnetic. The measured values for the Cu(I1) and Co(I1)

complexes are 1.75 B.M. and 2.40 B.M., respectively, which corresponds to a single

electron. These values also show that the Ni(II) and Cu(I1) complexes are of' square-

planar structure and that the Co(II) complexes are of octahedral structure6,16-22 (Fig.2).

EXPEIUMENTAL

All reagents were purchased from Merck (Germany) or Fluka (Switzerland), and

used without further purification. ?'he elemental analyses (C, H, and N) have been

determined by using a Carlo-Ebra 1106 model analyser. The magnetic moments of the

complexes were measured according to the Gouy method on a Newport Instrument type

D-104 magnet power supply. *H NMR spectra were recorded on a Varian T 100-A

model spectrophotometer, IR spectra on a Pye-TJnicam SP 1025 model instrument using

KBr pellets, and the atomic absorption spectra (AAS) on a Varian AA-175 iustrument

and pH on an Orion model 420A p€I meter.

Svnthesk of Substbred P h e n v C ~ r o u h ~ ~ ~ OXit?WSl

In this study, l,2-phenylenebir(amino-pchiorophenylglyoxime) L*Hz, 13-

naphthylenebis(amin0-pchlorophenylglyoxime) L2H2, 3,4-tolylenebis(amino-pchloro-

phenylglyoxime) L3H2 and 2,6-pyridylbir(amino-pchlorophlenylglyoxime) L4H2 have

been synthesized from a&-pchlorophenylchloroglyoxime and the corresponding

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bis(AMIN0-p-CHLOROPHENYLGLYOXIME) COMPLEXES 46 1

C-N v v

1650

1650

1650

1650

1640

1650

1620

1640

1630

______ 1640

1630

1630

Table V: Magnetic Moments and Characteristic IR Bands of the Complexes as KBr Pellets (cm-1).

N O

980

950

980

980

950

940 ~-

980

960

950 .-

loo0

980

9R0

-

0 - P O V

1720

1130

1700

.~ 1730

1715

1130

1740

1710

1710

___

1740

1150

11 10

--

aromatic diamhes. &ti-pchlorophenylglyoxime was prepared according to the

literatmes-'2,'4.'5.

A solution of 0.01 mol of the appropriate aromatic diamine compound [1,2-

phenylenediamine (1.08 g), or 1,5-naphthyldiamine (1.58 g), or 3,4-diaminotoluene

(1.22 g), or 2,6-diaminopyridine (1.09 g)] in 40 mL absolute ethanol was added

dropwise over 30 minutes to a stirred solution of 4.66 g (0.02 mol) of m-p- chlorophenylchloroglyoxime in 60 mL absolute ethanol at -1OoC. The reaction mixture

was stirred for further 2-3 h, left overnight at OOC, and then diluted with 100-120 ml.

water. The precipitate obtained was filtered and then recrystallized from ethanol-water

(1 : 1). The crystalline product was filtered, washed with water, and dried in a vacuum

oven.

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462 PEKACAR, MERCIMEK, AND OZCAN

The ligands were found to be soluble in ethanol, DMF, DMSO and slightly soluble

in acetone and insoluble in water. The colors, yields, melting points, elemental analyses,

1H NMR and IR data of these ligands are given in Tables I, II and I", respectively.

Svnthesis ofthe C d l l ) . Ni(IIj and Co(IIj C o m l a e s

A solution of 1 mmol metal salt (NiC12. 6H2O ( 0.238 g 1; or CuCI2. 2H20

(0.172 g); or CoC12. 6H2O (0.238 g) ] in 20 mL of water-ethanol (2:l) was added to a

solution of 1 mmol of the ligand [ L1H2 ( 0.501 g ); or L2H2 ( 0.551 g ); or L3H2

( 0.515 g ); or L4H2 ( 0.502 g) 1, dissolved in 40 mL of ethanol. The pH of the mixture

was 3.0-3.5 and its color turned to red-brown or dark-brown. After addition of 1%

NaOH solution in ethanol-water fl:1) to increase the pH to 4.5-5.0, the mixture was

stirred on a water-bath at SO-6O0C for 20 minutes. The precipitated complexes were

filtered while hot, washed with water, ethanol and diethyl ether, and then dried in a

vacuum oven. The colors, yields, melting points, elemental analytical results, magnetic

moments of the complexes and JR data of the compounds are given in Tables IV and V,

respectively.

REFERENCES

1. G. hez and 0. Bekaroglu, Synth. React. Inorg. Mct.-Org. Chem., 12, 781 (1983).

2. A. Giil and 0. Bekarogly J. Chem. Soc. Dalton Trans., 2537 (1983).

3. K. KaradeNz and 6. Bekaroglu, Synth. React. Inorg. Met.-Org. Chem., 13,

4. Y. Gok and 0. Bekarogly Synth. React. Inorg. Met.-Org. Chem., 13,675 (1988)

5. E. Ozcan and R. ~ ~ a o ~ l u , Synth. React. Inorg. Met.-Org. Chem., 18,559 (1988).

6. V. Ahsen and 6. Bekaroglu, Synth. React. Inorg. Met.-Org. Chem., l5, 61 (1985).

7. V. Ahsen, A. Giil, A. Giirek and 0. Bekarogu, J. Chem. Soc. Dalton Trans.,

1029 (1983).

5 (1990).

8. H. I. U w and R. Mirzaoglu, Synth. React. Inorg. Met.-Org. Chem., 20, 437 (1990).

Dow

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bis(AMINO-p-CHLOROPHENY LGLYOXIME) COMPLEXES 463

9. H. I. Ugan and R. Mirzaoglu, Synth. React. Inorg. Met.-Org. Chem., 2, 1083 (1991).

10. A. I. Pekacar and E. Ozan, Macromolecular Reports, A 31 (Suppl.5),

11. A. I. Pekacar and E. Ozcan, Macromolecular Reports, A 32 (Suppl.8),

12. A. I. Pekacar and E. Ozcan, Synth. React. Inorg. Met.-Org. Chem., 25,859 (1995).

13. B. Mercimek, E.0zcan and A. I. Pekacar, Synth. React. Inorg. Met.-Org. Chem.,

651 (1994).

1161 (1995).

_I 25. 1571 (1995).

14. H. C. Sevindir andR. Mirzaoglu, Synth. React. Inorg. Met.-Org. Chem., 22, 851 (1992).

15. H. C. Sevindir and R. Mirzaoglu, Synth. React. Inorg. Met.-Org. Chem., 2, 1129 (1992).

16. M. Kogak and 0. Bekaroglu, Synth. React. Inorg. Met.-Org. Chem., l4, 689 (1984).

17. F. A. Cotton and G. Wilkinson, "Advanced Inorgaruc Chemistry",

18. V. Ahsen, A. Gulek, A. Giil and 0. Bekaroglu, J. Chctn. SOC. Dalton Trans.,

Wiley-Interscience, New York (1988).

5 (1990).

19. B.Mercimek and G. hez, Macromolecular Reports, A 32 (Suppl.1-2), 147-1 53 (1995).

20. B.Mercimek ,G. Irez, M.A. Deveci, A.D.Bediik, N.Sankavakhand 1.Upn Macromolecular Reports, A 32 (Suppl.8), 1199-1206 (1995).

21. i.Karakq, H. I. Uqan and G. Irez, Chimica Acta Turcica 20 (1992).

22. I.Karaq, G. hez, M. Sezgin, H. I. Uqan and A. D. Bedilk, Synth. React. Inorg. Met-Org. Chem, 21, 1031-1041689 (1991). D

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