Synthesis and characterization of nickel(II), zinc(II), and cadmium(II) mixed-ligand complexes with 2,2′-bipyridylamine and phenols

Article abstract of DOI:10.1081/SIM-120016461

The present investigation reports the synthesis of mixed-ligand complexes of the type MAL, where M = Ni(II), Zn(II), Cd(II) A = 2,2′-bipyridylamine and H₂L¹ = catechol, H₂L₂ = pyrogallol, H₂L³ = 2,3-dihydroxynaphthalene, H₂L⁴ = protocatechuic acid. Their structures have been elucidated on the basis of elemental analyses, conductivity, thermogravimetric, magnetic moments and IR spectroscopy. The results are in accord with an octahedral environment around the central metal ions except for Ni(II). All chelates are diamagnetic. A study of the thermal properties has also been carried out.

Full text of DOI:10.1081/SIM-120016461

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Synthesis and Reactivity in Inorganic and Metal-Organic
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SYNTHESIS AND CHARACTERIZATION OF NICKEL(II),
ZINC(II), AND CADMIUM(II) MIXED-LIGAND COMPLEXES
WITH 2,2′-BIPYRIDYLAMINE AND PHENOLS
J. D. Joshi a , Sangita Sharma a , Gautam Patel a & J. J. Vora a
a Department of Chemistry , Sardar Patel University , Vallabh Vidyanagar, Gujarat, 388120,
India
Published online: 15 Feb 2007.
To cite this article: J. D. Joshi , Sangita Sharma , Gautam Patel & J. J. Vora (2002) SYNTHESIS AND CHARACTERIZATION OF
NICKEL(II), ZINC(II), AND CADMIUM(II) MIXED-LIGAND COMPLEXES WITH 2,2′-BIPYRIDYLAMINE AND PHENOLS, Synthesis and
Reactivity in Inorganic and Metal-Organic Chemistry, 32:10, 1729-1741, DOI: 10.1081/SIM-120016461
To link to this article: http://dx.doi.org/10.1081/SIM-120016461
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©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 32, No. 10, pp. 1729–1741, 2002
SYNTHESIS AND CHARACTERIZATION
OF NICKEL(II), ZINC(II), AND
CADMIUM(II) MIXED-LIGAND
COMPLEXES WITH 2,20-
BIPYRIDYLAMINE AND PHENOLS
J. D. Joshi,* Sangita Sharma, Gautam Patel, and
J. J. Vora
Department of Chemistry, Sardar Patel University,
Vallabh Vidyanagar 388120, Gujarat, India
ABSTRACT
The present investigation reports the synthesis of mixed-
ligand complexes of the type MAL, where M ¼ Ni(II), Zn(II),
Cd(II) A ¼ 2,20-bipyridylamine and H2L1 ¼ catechol, H2L2 ¼
pyrogallol, H2L3 ¼ 2,3-dihydroxynaphthalene, H2L4 ¼ proto-
catechuic acid. Their structures have been elucidated on the
basis of elemental analyses, conductivity, thermogravimetric,
magnetic moments and IR spectroscopy. The results are in
accord with an octahedral environment around the central
metal ions except for Ni(II). All chelates are diamagnetic.
A study of the thermal properties has also been carried out.
*Corresponding author. E-mail: jdjoshi@indiatimes.com
1729
DOI: 10.1081=SIM-120016461
Copyright # 2002 by Marcel Dekker, Inc.
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com

1730
JOSHI ET AL.
INTRODUCTION
An extensive review of the literature reveals that mixed-ligand com-
plexes serve as suitable models for valuable information in the elucidation of
enzymatic processes of biological relevance.[174] The presence of transition
metals in human blood plasma indicates their importance in the mechanism
for accumulation, storage and transport of transition metals in living
organisms.[577] Antimicrobial activities of Ni(II), Zn(II), Cd(II) ions have
been reported.[879] The activity of nickel is known because it is a component
of a hydrolase[10] (urease) and it activates the genes of hydrogenases.[11] Zinc
participitates in many hydrolytic reactions and in the control of gene activity
by proteins with fingers.[12] Transition metals play a key role in biological
systems such as cell division, respiration, nitrogen fixation and photo-
synthesis.[13] This biological importance has encouraged us to synthesize and
study new heterochelates of Ni(II), Zn(II), Cd(II). These complexes are also
good bactericides and fungicides.[14]
In the current communication are reported, the heterochelates of
Ni(II), Zn(II), Cd(II) with 2,20-bipyridylamine and phenols such as catechol,
pyrogallol, 2,3-dihydroxynaphthalene or protocatechuic acid.
EXPERIMENTAL
Materials
The phenols were of BDH Analar grade. The primary ligand 2,20-
bipyridylamine was obtained from Fluka. Stock solutions of Ni(II), Zn(II),
and Cd(II) perchlorates were prepared and standardized by complexometic
methods.[15]
Preparation of Complexes
The synthesis of the complexes was carried out by mixing 10 mL of a
0.1 M aqueous solutions of Ni(II), Zn(II), or Cd(II) perchlorates with 10 mL
of a 0.1 M solution of 2,20-bipyridylamine in ethanol. After stirring this
mixture for 577 min, 10 mL of a 0.1 M solution of the phenol in ethanol was
added slowly with constant stirring. There was no immediate precipitation.
The pH of the above solutions was then raised to ꢀ7.0 using 0.1 M sodium
hydroxide solution which resulted in the precipitation of solids. The com-
plexes thus obtained were washed well with a 1:1 mixture of absolute alcohol

CADMIUM(II) MIXED-LIGAND COMPLEXES
1731
and water to remove unreacted metal salt and ligand. All complexes were
ꢁ
dried at room temperature at 27 C and kept in a vacuum desiccator.
Analyses and Physical Measurements
Elemental analyses were performed with a Coleman C, H, N analyzer.
The metal content was determined[16] by titration with a solution of stan-
dardized disodium salt of EDTA after decomposing the complexes with a
mixture of concentrated hydrochloric acid, nitric acid, perchloric acid and
sulfuric acid in 5:2:3:2 mL ratio, respectively. Magnetic susceptibilities were
measured by the Gouy method[17] at room temperature using Hg[Co(CNS)4]
as calibrant. The IR spectra were recorded on a Perkin-Elmer model 983
spectrophotometer in KBr pellets. The UV-Visible reflectance spectra were
measured on a Beckman DK-2A spectrophotometer using MgO as refer-
ence. Thermal measurements were performed using a Du Pont thermal
ꢂ1
ꢁ
analyser at a 10 C min heating rate.
RESULTS AND DISCUSSION
The analytical data of the complexes presented in Table I indicate
1:1:1 stoichiometry. The general equation for the formation of the complex
with catechol is shown as below.
M
2þ þ A þ H2L ! ½MALꢃ þ 2Hþ
L ¼ L1, L2, L3 and L4
All of the chelates possess high decomposition points and are colored,
except the [Zn(A)(protocatechuic acid)] complex which is white. All are
amorphous and stable in air. The chelates are partially soluble in ethanol
and insoluble in water and other organic solvents. Hence, it was not possible
to characterize them by conventional methods like osmometry or viscosity
measurements.
Conductance Measurements
The complexes were found to be partially soluble in alcohol
and insoluble in water and other organic solvent. The conductivity of

1732
JOSHI ET AL.

CADMIUM(II) MIXED-LIGAND COMPLEXES
1733

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ꢌꢂꢀꢃꢄ ꢅꢁꢂꢄꢃꢀꢂꢈ ꢋꢂꢍꢂ ꢅꢃꢍꢍꢇꢂꢎ ꢆꢉꢀ ꢇꢊ ꢃꢇꢍ ꢓꢒ ꢁꢂꢃꢀꢇꢊꢏ ꢃꢀ ꢃ ꢅꢆꢊꢈꢀꢃꢊꢀ ꢍꢃꢀꢂ ꢆꢗ ꢙ0 ꢁC
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ꢂꢌꢕꢄꢆꢒꢂꢎ ꢇꢊ ꢀꢁꢂꢈꢂ ꢃꢊꢃꢄꢒꢈꢂꢈꢝ ꢀꢁꢂ ꢅꢆꢌꢕꢄꢂꢖꢂꢈ ꢄꢆꢈꢀ ꢋꢂꢇꢏꢁꢀ ꢏꢍꢃꢎꢉꢃꢄꢄꢒ ꢎꢉꢍꢇꢊꢏ
ꢂꢑꢂꢍꢒ ꢕꢁꢃꢈꢂ ꢆꢗ ꢀꢁꢂ ꢂꢖꢕꢂꢍꢇꢌꢂꢊꢀꢝ ꢀꢁꢂꢊ ꢀꢁꢂ ꢈꢃꢌꢕꢄꢂꢈ ꢉꢊꢎꢂꢍꢋꢂꢊꢀ ꢃꢊ ꢃꢅꢅꢂꢄꢂꢍꢃꢀꢂꢎ
ꢁ
ꢋꢂꢇꢏꢁꢀ ꢄꢆꢈꢈ ꢃꢊꢎꢝ ®ꢊꢃꢄꢄꢒꢝ ꢇꢊ ꢀꢁꢂ ꢀꢂꢌꢕꢂꢍꢃꢀꢉꢍꢂ ꢍꢃꢊꢏꢂ ꢆꢗ ꢃꢓꢆꢉꢀ 500ꢁ600 C ꢀꢁꢂ

CADMIUM(II) MIXED-LIGAND COMPLEXES
Table II. Infrared Spectra of the Metal Complexes (cmꢂ1 a
n(N7H) n(O7H) n(C7H) n(C¼C) n(C¼N) n(M7N) n(M7O)
1735
)
Compound
A
3420 b
7
3050 b 1600 s
1570 m
3050 b 1600 s
1670 m
7
7
[NiAL1]ꢄH2O 3420 b
3400 b
1650 m
780 s
430 s
1560 m 1630 m
1520 m
[NiAL2]ꢄH2O 3420 b
[NiAL3]ꢄH2O 3420 b
[NiAL4]ꢄH2O 3420 b
[ZnAL1]ꢄH2O 3420 b
[ZnAL2]ꢄH2O 3420 b
[ZnAL3]ꢄH2O 3420 b
[ZnAL4]ꢄH2O 3420 b
3400 b
3400 b
3400 b
3450 b
3400 b
3050 b 1580 s
1640 m
1640 m
1640 m
780 s
750 s
780 s
750 s
780 s
750 s
760 s
430 s
440 s
1520 s
3050 b 1590 s
1530 m
3050 b 1590 s
1530 m
3050 b 1600 m 1670 m
1570 s
3050 b 1600 s
1570 m
440 s
430 m
430 w
470 m
450 w
1670 m
770 s
760 s
760 s
3450 b 3050 w 1600 m 1650 m
1550 s
3400 b 3050 w 1600 s
1580 m
1670 m
[CdAL1]ꢄH2O 3420 b
3400 b
3400 b
3200 b 1580 s
1650 m
760 s
640 s
420 m
420 m
[CdAL2]ꢄH2O 3420 b
3200 b 1580 w 1650 m
1620 s
3400 b 3200 m 1580 w 1640 m
[CdAL3]ꢄH2O 3420 b
[CdAL4]ꢄH2O 3420 b
640 s
640 s
480 m
480 m
1620 s
3400 b 3200 m 1580 w 1640 s
1620 s
ab ¼ broad, m ¼ medium, s ¼ strong, w ¼ weak, A ¼ 2,20-bipyridylamine; L1 ¼
catechol dianion; L2 ¼ pyrogallol dianion; L3 ¼ 2,3-dihydroxynapthalene dianion;
L4 ¼ protocatechuic acid dianion.
rate of weight loss became much more moderate. During the initial phase
the gradual weight loss is due to water. In general, the water of hydration
may be considered either as crystal or coordinated water. According to
Nikolaev et al.[27] water eliminating below 150 ꢁC can be considered as
crystal water and water eliminated above 150 ꢁC may be due to coordination
to the metal ion. The nature of the water observed in the complexes is water
of crystallization, as reported in our previous publications.[28]
Thermogravimetric data of the primary ligand 2,20-bipyridylamine and
the metal chelates are presented in Table III. The cumulative weight losses

1736
JOSHI ET AL.

CADMIUM(II) MIXED-LIGAND COMPLEXES
1737
Table IV. Watꢁer Content at 25 ꢁC and Cumulative Weight Loss Data of Metal
ꢁ
Chelates at 100 C and 150 C
Found
ꢁ
ꢁ
ꢁ
150 C
H2O 25 C
100 C
Compounda
g
%
g
%
g
%
[NiAL1]ꢄH2O
[NiAL2]ꢄH2O
[NiAL3]ꢄH2O
[NiAL4]ꢄH2O
[ZnAL1]ꢄH2O
[ZnAL2]ꢄH2O
[ZnAL3]ꢄH2O
[ZnAL4]ꢄH2O
[CdAL1]ꢄH2O
[CdAL2]ꢄH2O
[CdAL3]ꢄH2O
[CdAL4]ꢄH2O
18.00
18.00
18.00
18.00
18.00
18.00
18.00
18.00
18.00
18.00
18.00
18.00
5.06
4.84
4.43
4.69
4.96
4.75
4.36
4.43
4.39
4.24
3.91
3.98
32.04
42.03
34.51
19.96
11.24
15.90
24.76
19.92
4.09
9.0
11.3
8.5
5.2
3.1
4.2
6.0
4.9
1.0
2.0
3.0
1.0
39.16
49.47
49.53
22.27
23.57
21.58
34.66
24.80
4.09
11.0
13.3
12.2
5.8
6.5
5.7
8.4
6.1
1.0
3.0
5.0
4.0
8.51
13.79
4.53
12.77
22.99
18.14
aA ¼ 2,20-bipyridylamine; L1 ¼ catechol dianion; L2 ¼ pyrogallol dianion; L3 ¼ 2,3-
dihydroxynapthalene dianion; L4 ¼ protocatechuic acid dianion.
of metal chelates at 100 ꢁC ꢁand 150 ꢁC are presented in Table IV along with
percentage of water at 25 C. Thermogravimetric analyses indicates elim-
ination of water and decomposition loss together. Therefore, higher per-
centage are observed in all the cases except [CdAL1]ꢄH2O and [CdAL2]ꢄ-
H2O at 150 ꢁC. The deviation is higher in case of Ni(II) and lower or negative
in case of Cd(II) complexes and may be due to the specific nature of metal ions.
Electronic Spectra and Magnetic Measurements
The information regarding geometry of these complexes is obtained
from their electronic spectral data and magnetic moments. The Ni(II)
complexes were found to be diamagnetic, as expected for four-coordinated,
square planar complexes.[29] The electronic spectra of the Ni(II) d8 com-
plexes exhibit absorptions at 15,630, 21,940 and 24,700 cmꢂ1 assigned to
1A1 ? 1A2 (n1)1, 1A1 ? 1B2 (n2), and 1A1 ? 1E1 transitions[30731] of Ni(II) in
a square-planar environment due to large crystal field splitting.
The Zn(II) and Cd(II) complexes are diamagnetic as expected for d10
systems.[32] Bands were obtained at 28,197 cmꢂ1, 29,431 cmꢂ1 (27,211),

1738
JOSHI ET AL.
Figure 1. Suggested structures of the complexes shown for catechol as the phenol.
28,984 cmꢂ1 and 29,449 cmꢂ1 (27,344) for the Zn(II) complexes and
25,157 cmꢂ1, 28,571 cmꢂ1 (24,968), 25,614 cmꢂ1 and 28,571 cmꢂ1 (25,477)
for the Cd(II) complexes with catechol, pyrogallol, 2,3-dihydroxy-
naphthalene or protocatechuic acid, respectively, are due to the ligands. The
molar intensity (in L moleꢂ1 cmꢂ1) is reported in parentheses. The absence
of intensity value may infer that the measurement was carried out by a
different technique. Three transitions are expected, (A1) ? p*(E),
(E) ? p*(A2) and (E) ? p*(E), but only one shoulder band is obtained. This
band may be either due to n ? p* or p ? p* transitions of the ligands or a
merger of both transitions.[33734]
CONCLUSIONS
On the basis of elemental analyses, IR, thermogravimetric analyses,
UV-Visible reflectance spectra and magnetic properties, it is possible to
assign square planar to the Ni(II) and octahedral geometry to the Zn(II) and
Cd(II) complexes as shown in Fig. 1. The values of b is favourable for
assigned structures. The structure assignment, however, can not be con-
sidered final in the absence of x-ray crystal studies.
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Received January 7, 2002
Accepted July 10, 2002
Referee I: R. M. Matthews
Referee II: W. R. Mason