Syntheses and characterization of 4-(11-chloro-3,6,9-trioxaundecyloxy)phenylaminoglyoxime and its complexes with copper(II), nickel(II), and cobalt(II)

Article abstract of DOI:10.1081/SIM-120003801

A novel vic-dioxime ligand containing ethyleneoxy groups, 4-(11-chloro-3,6,9-trioxaundecyloxy)phenylaminoglyoxime (LH₂) has been prepared from 1-amino-4-(11-chloro-3,6,9-trioxaundecyloxy)benzene and monochloro anti-glyoxime. Its complexes, Ni(LH)₂, Cu(LH)₂ and Co(LH)₂, have been synthesized. The analytical data show that the metal to ligand ratio in the complexes is 1:2. The complexes are formed by coordination of N,N atoms of the ligand. The structures of the oxime ligand (LH₂) and its complexes were elucidated by ¹H NMR, IR, UV.-Visible and elemental analyses techniques.

Full text of DOI:10.1081/SIM-120003801

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SYNTHESES AND CHARACTERIZATION OF 4-(11-
CHLORO-3,6,9-TRIOXAUNDECYLOXY) PHENYLAMINO-
GLYOXIME AND ITS COMPLEXES WITH COPPER(II),
NICKEL(II), AND COBALT(II)
Mükerrem Kurtogˇlu a & Selahattin Serin a b
a Department of Chemistry , University of Kahramanmaraş Sütçü İmam , Kahramanmaraş,
46100, Turkey
b Department of Chemistry , University of Çukurova , Adana, 01330, Turkey
Published online: 15 Feb 2007.
To cite this article: Mükerrem Kurtogˇlu & Selahattin Serin (2002) SYNTHESES AND CHARACTERIZATION OF 4-(11-
CHLORO-3,6,9-TRIOXAUNDECYLOXY) PHENYLAMINO-GLYOXIME AND ITS COMPLEXES WITH COPPER(II), NICKEL(II), AND
COBALT(II), Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 32:3, 629-637, DOI: 10.1081/SIM-120003801
To link to this article: http://dx.doi.org/10.1081/SIM-120003801
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SYNTH. REACT. INORG. MET.-ORG. CHEM., 32(3), 629–637 (2002)
SYNTHESES AND CHARACTERIZATION
OF 4-(11-CHLORO-3,6,9-
TRIOXAUNDECYLOXY)PHENYLAMINO-
GLYOXIME AND ITS COMPLEXES
WITH COPPER(II),
NICKEL(II), AND COBALT(II)
1
kerrem Kurtoglu and Selahattin Serin
1,2,
˘
Mu
¨
*
1Department of Chemistry, University
_
of Kahramanmaras
¸
Sutc
¸
u Imam, 46100,
¨
, Turkey
¨
Kahramanmaras
¸
2Department of Chemistry, University of C
¸ ukurova,
01330, Adana, Turkey
ABSTRACT
A novel vic-dioxime ligand containing ethyleneoxy groups,
4-(11-chloro-3,6,9-trioxaundecyloxy)phenylaminoglyoxime
(LH2) has been prepared from 1-amino-4-(11-chloro-3,6,9-
trioxaundecyloxy)benzene and monochloro anti-glyoxime. Its
complexes, Ni(LH)2, Cu(LH)2 and Co(LH)2, have been syn-
thesized. The analytical data show that the metal to ligand
ratio in the complexes is 1:2. The complexes are formed by
*Corresponding author. E-mail: mkurtoglu@ksu.edu.tr
629
Copyright # 2002 by Marcel Dekker, Inc.
www.dekker.com

˘
KURTOGLU AND SERIN
630
coordination of N,N atoms of the ligand. The structures of
the oxime ligand (LH2) and its complexes were elucidated by
1H NMR, IR, UV.-Visible and elemental analyses techniques.
INTRODUCTION
Vic-dioximes have received considerable attention as model com-
1,2
pounds which mimic biofunctions such as the reduction of vitamin B12
Oxime metal chelates are biologically active and semiconducting3.
.
The coordination chemistry of vic-dioximes is an intensive area of
study and numerous transition metal complexes of this group of ligands
have been investigated476. The presence of mildly acidic hydroxy groups and
slightly basic nitrogen atoms make vicinal dioximes amphoteric ligands
which form corrin-type, square-planar, square-pyramidal or octahedral
complexes with transition metal ions such as copper(II), nickel(II), palla-
dium(II), cobalt(II) and cobalt(III) as central atoms7,8. The exceptional
stability and unique electronic properties of these complexes can be attribu-
ted to their planar structure which is stabilized by hydrogen bonding. The
high stability of the complexes prepared with vic-dioxime ligands has been
extensively used for various purposes, including model compounds for
vitamin B12 or trace metal analyses9.
In the present study, we report the syntheses and complex formation
of 4-(11-chloro-3,6,9-trioxaundecyloxy)phenylaminoglyoxime (LH2) which
was synthesized by the reaction of l-amino-4-(3,6,9-trioxaundecyloxy)-
benzene with monochloro anti-glyoxime at room temperature. The reaction
of l-amino-4-(3,6,9-trioxaundecyloxy)benzene with monochloro anti-glyox-
ime may be represented as shown in Fig. 1. We examined its complexing
ability with Ni(II), Cu(II) and Co(II) salts.
EXPERIMENTAL
Materials
1-Amino-4-(11-chloro-3,6,9-trioxaundecyloxy)benzene10 and mono-
chloro anti-glyoxime were prepared according to the literature11.
NiCl2ꢀ6H2O, CuCl2ꢀ2H2O and CoCl2ꢀ6H2O (Merck) were used as pur-
chased. All solvents were reagent grade and used without further purifica-
tion. IR spectra were recorded on a Shimadzu FT-IR 8300 spectrometer.
The electronic absorption spectra of ethanol solutions of the ligand
and complexes in the range 2007800 nm were measured on a Shimadzu

COMPLEXES WITH Cu(II), Ni(II), AND Co(II)
631
Figure 1. Synthesis reaction of 4-(11-Chloro-3,6,9-trioxaundecyloxy)phenylamino-
glyoxime.
UV-160A spectrometer. The elemental analyses and 1H NMR spectra of the
ligand were determined at TUBITAK (Center of Science and Technology
Research of Turkey).
Synthesis of 4-(11-Chloro-3,6,9-
trioxaundecyloxy)phenylaminoglyoxime, LH2
A solution of l-amino-4-(11-chloro-3,6,9-trioxaundecyloxy)benzene
(0.400 g, 1.318 mmol) in 25 mL of alcohol was added dropwise with stirring
into a solution of monochloro anti-glyoxime (0.161 g, 1.318 mmol) in 35 mL
of methylene chloride at room temperature. Stirring was continued for 11=2 h
after the precipitation started. A quantity of 15 mL of cold ethanol was added
and the precipitate was filtered and washed with cold ethanol and dried in

˘
KURTOGLU AND SERIN
632
vacuo; it is soluble in hot ethanol, DMSO and DMF and slightly soluble in
ꢁ
chloroform and water. Yield, 0.395 g (77%); M. p.: 63765 C. Elemental
Analyses for C16H24N3ClO6 (MW 389.5 g=mol); Calcld. (%): C, 49.29; H,
6.16; N, 10.78. Found (%): C, 49.47; H, 6.03; N, 10.91. IR (KBr, cmꢂ1): 3440
m (N-H), 3180 s (O-H), 3045 w (Ar-C-H), 2960 s (-CH2CH2-), 1640 m (C¼N),
1
1225 s (Ar-O-C), 1118 s (C-O-C). UV-Vis. (lmax, nm): 385, 290, 272. H
NMR (DMSO-d6): 3.5573.65 (m, 2 H, -CH2CI), 3.6573.75 (m, 10 H, g-Z-
CH2), 3.86 (t, J ¼ 4.8, 2 H, b-CH2), 4.15 (t, J ¼ 4.8 Hz, 2 H, a-CH2), 6.6076.75
(m, 4 H, Ar-H), 8.30 (s, 1 H, HC¼N), 9.20 (s, 1 H, NH), 10.85 (s, 2 H, OH).
Synthesis of Bis[4-(11-chloro-3,6,9-
trioxaundecyloxy)phenylaminoglyoximato]nickel(II), Ni(LH)2
A solution of NiCl2ꢀ6H2O (0.125 g, 0.53 mmol) in ethanol (20 mL) was
added to a solution of LH2 (0.412 g, 1.05 mmol) in hot ethanol (10 mL). The
reaction mixture was stirred at 45 ꢁC for 3 1=2 h. A 0.1 M solution of NH3 in
alcohol (10 mL) was then added (pH ¼ 3.5) and the resulting precipitate was
filtered, washed with water and ethanol and dried. Yield, 0.713 g (80%); M. p.:
ꢁ
1457147 C. Elemental Analyses for C32H46N6Cl2O12N (MW 835.5 g=mol);
Calcld. (%):C, 45.96;H, 5.51;N, 10.05. Found(%):C, 46.09;H, 5.64;N, 10.25.
IR (KBr, cmꢂ1): 3430 m (N-H), 3050 w (Ar-C-H), 2960 s (-CH2CH2-), 1640 w
(C¼N), 1225 s (Ar-O-C), 1118 s (C-O-C). UV-Vis. (lmax, nm): 390, 285, 270.
Synthesis of Bis[4-(11-chloro-3,6,9-
trioxaundecyloxy)phenylaminoglyoximato]copper(II), Cu(LH)2
LH2 (0.389 g 1.0 mmol) was dissolved in 10 mL of ethanol. To this
solution was added a solution of CuCl2ꢀ2H2O (0.085 g, 0.5 mmol) in ethanol
(10 mL). While stirring and heating, a 0.1 N solution of NaOH in ethanol
was added until the pH became 4.5 and then was heated on a water bath for
4 h. The dark brown complex was filtered, washed with alcohol and ether,
then dried in vacuo. Yield, 0.70 g (83%); M. p.: 1337134 ꢁC; meff.: 1.82 B. M.
Elemental Analyses for C32H46N6Cl2O12Cu (MW 840.5 g=mol); Calcld.
(%): C, 45.68; H, 5.47; N, 9.99. Found (%): C, 45.77; H, 5.53; N, 9.78. IR
(KBr, cmꢂ1): 3435 w (N-H), 3035 w (Ar-C-H), 2964 s (-CH2CH2-), 1642 w
(C¼N), 1225 s (Ar-O-C), 1120 s (C-O-C). UV-Vis. (lmax, nm): 410, 380, 285.
Synthesis of Bis[4-(11-chloro-3,6,9-
trioxaundecyloxy)phenylaminoglyoximato]cobalt(II), Co(LH)2
LH2 (0.389 g, 1 mmol) was dissolved in 10 mL of ethanol and to this
solution was added a solution of CoCl2ꢀ6H2O (0.119 g, 0.5 mmol) in ethanol

COMPLEXES WITH Cu(II), Ni(II), AND Co(II)
633
(10 mL). The solution was treated with a 0.1 N NaOH solution in alcohol
until the pH became 4.5. Then the mixture was heated on a water bath for
4 h and allowed to stand overnight. The brown complex was precipitated
with ether. The product was dried in vacuo. Yield, 0.625 g (77%); M. p.:
ꢁ
1587160 C; meff.: 2.12 B. M. Elemental Analyses for C32H46N6Cl2O12Co
(MW 836 g=mol); Calcld. (%): C, 45.93; H, 5.50; N, 10.05. Found (%): C,
46.07; H, 5.41; N, 10.17. IR (KBr, cmꢂ1): 3450 w (N-H), 3047 w (Ar-C-H),
2958 s (-CH2CH2-), 1637 w (C¼N), 1224 s (Ar-O-C), 1117 s (C-O-C). UV-
Vis. (lmax, nm): 405, 383, 261.
RESULTS AND DISCUSSION
The synthesis of 4-(l1-chloro-3,6,9-trioxaundecyloxy)phenylaminoglyox-
ime, the vic-dioxime ligand LH2, is described in Fig. 1. The vic-dioxime was
obtained in 77% yield by reacting monochloro anti-glyoxime with 1-amino-4-
(11-chloro-3,6,9-trioxaundecyloxy)benzene. The structure of LH2 was deter-
1
mined by a combination of elemental analyses, H NMR, IR and UV-Vis.
spectral data.
The reaction of the vic-dioxime ligand with NiCl2ꢀ6H2O, CuCl2ꢀ2H2O,
CoCl2ꢀ6H2O salts give product with a metal ligand ratio of 1:2 according to
elemental analysis data. The Ni(II), Cu(II) and Co(II) complexes of the LH2
vic-dioxime ligand have been isolated and their structures have been
investigated. The formation of these complexes is shown by the following
general equation.
MCl2 ꢀmH2O þ 2LH2ꢂ! MðLHÞ þ mH2O þ 2HCl
M ¼ NiðIIÞ; CuðIIÞ or CoðIIÞ 2
LH2 ¼ 4-ð11-chloro-3;6;9-trioxaundecyloxyÞphenylaminoglyoxime
1
The H NMR spectrum of LH2 in DMSO-d6 resulted in peaks cor-
responding to the aromatic protons at 6.63 ppm and 675 ppm as doublets.
In the spectrum of LH2 the N-H protons next to the oxime groups are a
singlet at 9.25 ppm. The singlet at 10.80 ppm is assigned to hydroxy protons
of vic-dioxime12,16. The spectrum also show three triplets at 3.5573.63 ppm,
3.80 ppm and 4.20 ppm for -CH2Cl, b-CH2- and a-CH2- protons, respec-
tively13,14. The other ether methylene protons appeared as multiplets at
3.6373.75 ppm. These results were consistent with those reported for oxy-
ethylene groups attached to a benzene ring as in crown ethers or
chains15717
.

˘
KURTOGLU AND SERIN
634
In the IR spectrum of LH2, the OH stretching vibrations are observed
at 3180 cmꢂ1 as a broad absorption. Bands due to N-H, C¼N and N-O
stretches are at 3440, 1640 and 1010 cmꢂ1, respectively, in good agreement
with values reported for similar compounds18. The bands at 1225 cmꢂ1 and
1118 cmꢂ1in the spectrum of LH2 correspond to the asymmetric and sym-
metric stretching of the C-O-C ether groups19,20. Aromatic C-H and ali-
phatic C-H bands occurred at 3045 cmꢂ1 and 2960 cmꢂ1. The Ni(LH)2,
Cu(LH)2 and Co(LH)2 complexes have IR spectra very similar to those of
LH2, except for the disappearence of the OH stretching frequencies. Weak
bands at ca. 1700 cmꢂ1 indicate OH-O bridges, while the C¼N vibrations
are at lower wave numbers, as expected for N,N-chelated vicinal dioxime
complexes.
The UV-Visible spectra of the vic-dioxime ligand and its metal com-
plexes, Ni(LH)2, Cu(LH)2 and Co(LH)2, were measured in ethanol. The
data of the ligand and the complexes are reported in the experimental part.
The UV.-Visible peaks corresponding to the C¼N group and the aromatic
ring in the vicdioxime ligand were observed at 385 nm and 290 nm. The
peaks belonging to the C¼N group in the spectra of the Ni(LH)2, Cu(LH)2
and Co(LH)2 complexes appeared at 390 nm, 380 nm and 383 nm,
respectively.
Magnetic susceptibility measurements provided sufficient data to
characterize the structures. The complex of Ni(II), Ni(LH)2 is diamagnetic
as expected for a d8 metal ion in a square-planar field21.
The magnetic moment value of 2.12 BM observed for the Co(II)
complex, Cu(LH)2, reveals a square-planar geometry around the Co(II) ion.
Figure 2. Proposed structure of the metal complexes.

COMPLEXES WITH Cu(II), Ni(II), AND Co(II)
635
The effective magnetic moment of 1.82 B.M. for Cu(II) complex suggested a
square-planar geometry around the Cu(II) ion22725
.
The synthesized complexes are suggested to have the general structural
formulas as shown in Fig. 2.
ACKNOWLEDGMENTS
This work was supported by the Research Fund of C
versity, Adana, Turkey (Project No: FBE.97.124). We are indebted to Dr.
Osman Serindag, Department of Chemistry, Cukurova University, Adana,
Turkey for assistance.
¸ ukurova Uni-
¸
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Received January 4, 2000
Accepted January 15, 2002
Referee I: A. I. Odom
Referee II: A. R. Oki