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Synthesis, spectroscopic and

electrochemical studies of copper(II)
and cobalt(II) complexes of three
unsymmetrical vic -dioximes ligands
a a a a
Esref Tas , Mehmet Aslanoglu , Ahmet Kilic & Zeliha Kara
a
Department of Chemistry , Harran University , Sanliurfa 63510,
Turkey
Published online: 25 Jan 2007.

To cite this article: Esref Tas , Mehmet Aslanoglu , Ahmet Kilic & Zeliha Kara (2006) Synthesis,
spectroscopic and electrochemical studies of copper(II) and cobalt(II) complexes of three
unsymmetrical vic -dioximes ligands, Journal of Coordination Chemistry, 59:8, 861-872, DOI:
10.1080/00958970500412206

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 Journal of Coordination Chemistry
Vol. 59, No. 8, 20 May 2006, 861–872

Synthesis, spectroscopic and electrochemical studies

of copper(II) and cobalt(II) complexes of three
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unsymmetrical vic-dioximes ligands

ESREF TAS*, MEHMET ASLANOGLU,
AHMET KILIC and ZELIHA KARA
Department of Chemistry, Harran University, Sanliurfa 63510, Turkey

(Received 17 March 2005; in final form 27 June 2005)

Cobalt(II) and copper(II) complexes with three dioxime ligands cyclohexylamine-

p-tolylglyoxime (L1H2), tert-butyl amine-p-tolylglioxime (L2H2) and sec-butylamine-
p-tolylglyoxime (L3H2), have been prepared. The metal to ligand ratios of the complexes
were found to be 1 : 2. The Cu(II) complexes of these ligands are proposed to be square
planar; the Co(II) complexes are proposed to be octahedral with water molecules as axial
ligands. Ligands and complexes are soluble in common solvents such as DMSO, DMF,
CHCl3 and C2H5OH. The ligands have been characterized by elemental analysis, IR,
UV-VIS, 1H NMR, 13C NMR and thermogravimetric analysis (TGA). The complexes were
characterized by elemental analysis, IR, UV-VIS, magnetic susceptibility measurements,
thermogravimetric analysis (TGA) and electrochemistry. Electrochemical properties of metal
complexes show quasi-reversible one-electron redox processes. However, Co(L1H)2 and
Cu(L1H)2 complexes show another oxidation peak in the positive region. This single irreversible
oxidation peak is caused by the cyclic ring of the ligand. Data also revealed that the electron
transfer rates of metal complexes with L1H2 are higher than the other complexes.

Keywords: vic-Dioxime; Co(II) and Ni(II) complexes; Synthesis; Structures;

Electrochemical properties

1. Introduction

The chemistry of oxime/oximato metal complexes has been investigated since prepara-
tion of nickel(II) dimethylglyoximato and recognition of the chelate five-membered
character of this complex by Chugaev [1]. Oximes are widely recognized as versatile
synthons for a variety of heterocycles [2]. The exceptional stability and unique elec-
tronic properties of these complexes can be attributed to their planar structure,
which is stabilized by hydrogen bonding [3]. When asymmetrical dioximes such as
phenylglyoxime or methylglyoxime are employed as starting ligands, usually a mixture

*Corresponding author. Email: [email protected]

Journal of Coordination Chemistry

ISSN 0095-8972 print: ISSN 1029-0389 online ß 2006 Taylor & Francis
DOI: 10.1080/00958970500412206
 862 E. Tas et al.

of fac- and mer-isomers was obtained. In a few cases one isomer could be isolated [4].
The synthetic chemistry of a MN4 core containing vic-dioxime compounds has been
described previously [5]. Metal-containing oxime complexes are utilized in medicine
as well; technetium(V) and copper(II) complexes containing vicinal dioxime are
currently used as cerebral and myocardial perfusion imaging agents [6].
Tas et al. have prepared vic-dioxime ligands, which have different substituents
on their transition metal complexes [7]. Gok et al. have synthesized aza compounds
attached to the dioxime group [8]. Other applications for these compounds concern
liquid crystals [9], gas sensors [10] and inhibitors for chemical warfare agents [11].
We report here the synthesis and structural properties of three new vic-dioxime
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containing three new ligands (L1H2, L2H2 and L3H2) and mononuclear complexes
with Cu(II) and Co(II). Electrochemistry of the mononuclear complexes has also
been investigated.

2. Experimental

Anti-p-tolylchloroglyoxime was synthesized as described in the literature [12].

Cyclohexylamine, tert-butylamine and sec-butylamine (Fluka Chemical Company,
Taufkirchen, Germany) and tetra-n-butylammonium perchlorate (n-Bu4NClO4, Fluka
Chemical Company, Taufkirchen, Germany) were used as received.
Elemental analyses were carried out in the Laboratory of the Scientific and Technical
Research Council of Turkey (TUBITAK). IR spectra were recorded on a Perkin-Elmer
Spectrum RXI FT-IR Spectrometer as KBr pellets, 1H NMR spectra were recorded on
a Varian XL-200. Magnetic susceptibilities were determined on a Sherwood Scientific
Magnetic Susceptibility Balance (Model MK1) at room temperature (20
C) using
Hg[Co(SCN)4] as a calibrant; diamagnetic corrections were calculated from
Pascal’s constants [13]. UV-VIS spectra were recorded on a Schimadzu 1601 PC.
An EcoChemie Autolab-12 potentiostat with the electrochemical software package
GPES 4.9 (Utrecht, The Netherlands) was used for voltammetric measurements.
A three electrode system was used: a platinum wire counter electrode, an Ag/AgCl
reference electrode and a 2 mm sized platinum disc electrode as working electrode.
The working electrode was polished with 0.05 mm alumina prior to each experiment.
Throughout the experiment oxygen-free nitrogen was bubbled through the solution
for 10 min. Voltammetric experiments were performed at room temperature.

2.1. Synthesis of the ligands L1H2, L2H2 and L3H2

Anti-p-tolylchloroglyoxime was synthesized as described in the literature [12].
A solution of 15.8 mmol of cyclohexylamine, 15.8 mmol t-butylamine and 15.8 mmol
secondarybutylamine in 30 cm3 of absolute THF was added to a solution of
15.8 mmol of Et3N in 10 cm3 of absolute THF. This mixture was cooled to 15
C
and kept at this temperature, and a solution of 15.8 mmol anti-p-tolylchloroglyoxime
in 50 cm3 absolute THF was added dropwise under a N2 atmosphere with continuous
stirring. The addition of the anti-p-tolylchloroglyoxime solution was carried out over
1.5 h. The mixture was stirred for 1 h more and the temperature raised to 20
C.
Precipitated Et3NHCl was filtered and the filtrate was evaporated to remove THF.
The oily products were dissolved in 10 cm3 of CH2Cl2 and 200 cm3 of n-hexane were
 Unsymmetrical vic-dioximes 863

added to precipitate the compound. This process was then repeated several times.
The products were filtered and dried in vacuum. The products are soluble in
common solvents such as CH2Cl2, CHCl3, Me2CO, THF, EtOH and DMSO. L1H2
characteristic 13C NMR chemical shift (CDCl3, TMS,
ppm): C1 (35.16 and 34.78),
C2 (140.00), C3 (126.67), C4 (129.00), C5 (133.93), C6 (149.30), C7 (148.67),
C8 (52.33), C9 (25.51), C10 (25.07) and C11 (21.64 and 21.77); L3H2 characteristic
13
C NMR the chemical shift (CDCl3, TMS,
ppm): C1 (31.10 and 31.06), C2 (139.84
and 140.05), C3 (127.47 and 126.73), C4 (129.27 and 128.95), C5 (130.61 and 130.00),
C6 (152.30), C7 (149.03 and 148.85), C8 (46.27), C9 (50.99 and 50.48) and
C10 (21.61–21.75 and 22.51–22.29).
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2.2. Synthesis of the cobalt(II) and copper(II) complexes

0.5 mmol L1H2, 0.5 mmol L2H2 or 0.5 mmol L3H2 was dissolved in EtOH (25 cm3).
A solution (0.25 mmol) of the metal salt [CoCl26H2O] or [CuCl22H2O] in 10 mL
of ethanol was added drop-wise with continuous stirring. The stirred mixture was
heated at reflux for 1 h and maintained at this temperature. The pH of solutions was
about 1.5–3.0 and was adjusted to 4.5–5.5 by the addition of a 1% NaOH solution
in ethanol. After cooling to room temperature, the complexes were filtered and
washed with hot water (3  5 mL), finally, washed with diethylether and dried at
90
C for 5 h. The products are soluble in solvents such as CHCl3 and DMSO.

3. Results and discussion

The routes for the synthesis of L1H2, L2H2 and L3H2 are given in scheme 1.
First, anti-p-tolylchloroglyoxime was synthesized as described in the literature [12].
Ligands (L1H2, L2H2 and L3H2), shown in figure 1, were prepared by reaction of
cyclohexylamine, tert-butylamine or sec-butylamine with a suspension of anti-
p-tolylchloroglyoxime in absolute THF with 15.8 mmol in solution of Et3N( triethyl-
amine) in absolute THF at 15
C. Excess Et3N( triethylamine) was used to neutralize
the HCl liberated in the reaction. The ligand has one cyclohexyl ring, one p-tolyl group
and two oxime groups for L1H2, one p-tolyl group, one tert-group and two oxime
groups for L2H2 and one p-tolyl group, one sec-group and two oxime groups

OH 3 4
(C2H5)3N 1 2 5 6 OH
R NH2 + H3C C N H3C C N
THF
Cl C N R NH C N
7
OH OH

10 9 CH3 CH3
11 9 10
8
R: H3C C H3C HC
, 8 , 9
CH3 CH2

Scheme 1. The structure of L1H2, L2H2 and L3H2

 864 E. Tas et al.

O H O

CH3 C=N N=C CH3

R NH C=N N=C NH R

O H O

M: Cu(II) and Co(II) . 2H2O

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CH3 CH3

R: , H 3C C , H C CH CH2
3

CH3

Figure 1. Structures of the Cu(II) and Co(II) complexes.

Table 1. The formulas, colors, melting points, yields, magnetic susceptibilities and elemental analyses of
the ligands and complexes.

Elemental analyses % calculated (Found)

m.p. Yield eff


Compounds Color C (dec.) (%) [BM] C H N

Ligand, L1H2 Pale 98 76 – 65.45 7.63 15.27

Yellow (65.20) (8.03) (15.12)
Brown 212 66 3.39 55.98 6.84 13.06
Co(L1H)2  2H2O (56.00) (6.95) (12.80)
Cu(L1H)2 Dark 210 71 1.54 58.87 6.54 13.73
Green (58.50) (6.71) (13.82)
Ligand, L2H2 Pale 67 64 – 62.65 7.63 16.86
Yellow (62.42) (8.15) (16.50)
Brown 225 79 3.69 52.79 6.76 14.21
Co(L2H)2  2H2O (52.54) (6.95) (14.60)
Cu(L2H)2 Dark 265 78 1.56 55.76 6.43 15.01
Green (56.00) (6.95) (14.80)
Ligand, L3H2 Pale 75 69 – 62.65 7.63 16.86
Yellow (62.90) (8.12) (16.69)
Dark 207 66 3.76 52.79 6.76 14.21
Co(L3H)2  2H2O Brown (52.54) (6.95) (14.40)
Cu(L3H)2 Dark 139 64 1.58 55.76 6.43 15.01
green (55.54) (6.75) (14.95)

for L3H2. Mononuclear complexes have been synthesized from L1H2, L2H2 and L3H2
with salts of Cu(II) and Co(II) with a metal–ligand ratio of 1 : 2. The ligands coordinate
by N,N0 atoms of vicinal dioximes. The cobalt(II) complex also has two coordinated
waters. These vic-dioximes form mononuclear complexes [14, 15].
The formulas, colors, melting points, yields, magnetic susceptibilities and elemental
analysis results of L1H2, L2H2 and L3H2 with their Cu(II) and Co(II) complexes
are listed in table 1. The structural formulas were deduced by elemental analysis, IR,
 Unsymmetrical vic-dioximes 865

Table 2. Characteristic IR bands (cm1) of the ligands and complexes as KBr pellets.

Compounds O–H N–H Aliph. C–H O–H  O N–O C¼N

Ligand, L1H2 3540–2557 3335 2930–2856 – 999 1647

Co(L1H)2  2H2O 3440–3078 3398 2928–2853 1716 967 1630
Cu(L1H)2 3680–3084 3365 2925–2853 1720 962 1613
Ligand, L2H2 3184 3350 2963–2867 – 999 1629
Co(L2H)2  2H2O 3463 – 2966–2865 – 958 1612
Cu(L2H)2 – 3399 2970–2859 – 973 1609
Ligand, L3H2 3351–3243 3388 2970–2872 – 994 1645
Co(L3H)2  2H2O 3268 3400 2964–2873 1724 972 1639
Cu(L3H)2 – 3357 2964–2870 1718 970 1641
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Table 3. Characteristic UV-VIS bands of the ligands and complexes in CHCl3, DMSO and C2H5OH.

Compounds Solvents Wavelength  max. (nm) log " (M1 cm1)

Ligand, L1H2 C2H5OH 251(4.87) 257(2.99) 311(2.27)

CHCl3 244(3.87) 272(3.68) 291(2.95) 307(2.24)
Co(L1H)2  2H2O C2H5OH 215(5.43) 239(5.38) 243(4.60) 259(4.20) 352(3.55) 459(2.72)
CHCl3 244(5.16) 271s(4.90) 416s(3.50) 634(2.66)
Cu(L1H)2 DMSO 388(4.76) 391(3.85) 550s(2.74)
Ligand, L2H2 C2H5OH 252(4.26) 291(3.00) 307(2.28)
CHCl3 243(4.52) 250(5.55) 260(4.37) 295(2.89) 314(21.7)
Co(L2H)2  2H2O DMSO 300(4.64) 697s(2.28)
CHCl3 246(6.22) 399(4.78) 488(4.11)
Cu(L2H)2 DMSO 300(4.74) 383(4.61) 676s(2.73)
Ligand, L3H2 C2H5OH 251(5.07) 257(4.46) 293(2.95) 310(2.20)
CHCl3 247(6.38) 252(5.68) 291(2.85) 343(2.12)
Co(L3H)2  2H2O C2H5OH 244(4.69) 257(4.52) 293(389) 459(3.16) 536(2.39)
CHCl3 245(5.20) 268(4.48) 342(3.81)
Cu(L3H)2 DMSO 393(4.54) 410s(4.14) 670s(2.68)
s: shoulder.

1
Table 4. H NMR spectraa of the ligands in CDCI3 in
(ppm).

Funct. group L1H2 L2H2 L3H2

a
OH – – –
Ar–CH3 2.35 (3H)s 2.2–2.4 (3H)t 2.33 (3H)s
Ar–CH– 7.1–7.13 (2H)d 7.1–7.7 (4H)m 7.53 and 7.55 ( ) , 7.64 and 7.66 ( )d,
d

7.26–7.64 (2H)d 7.09 and 7.11 ( )d, 7.19 and 7.25 ( )d 4H

–CH 2.83 (1H)s – 2.91–3.10 (1H)b
–CH2 1.02 (4H)s – 1.13–1.31 (2H)m
1.4–1.8 (6H)m
C–CH3 – 1.1–1.4 (9H)m 0.64–0.71 (3H)m
0.88–0.90 ( )d and 0.96–0.98 ( )d 3H
NH– 5.2 (1H)b 5.3 (1H)b 5.27 and 5.05 (1H)b
m: multiplet, s: singlet, d: doublet, t: triplet, a: deuterium exchangeable, b: broad bands.

1
H NMR, 13C NMR, UV-VIS spectroscopic and cyclic voltammetry. Additional
analytical data are given in tables 1–5.
The interaction of the ligands L1H2, L2H2 and L3H2 with copper(II) salts yields
complexes corresponding to the general formula [M(LxH)2] and [(LxH)2M  2H2O]
for cobalt(II).
 866 E. Tas et al.

Table 5. Voltammetric data for Co(II) and Cu(II) complexes.

a
Complex Epa (V) Epc (V)
Ep (mV) Epa (V)

Co(L1H)2 1.27 1.50 230 0.19

Co(L2H)2 1.26 1.57 310
Co(L3H)2 1.28 1.55 270
Cu(L1H)2 0.27 0.16 110 0.57
Cu(L2H)2 0.42 0.23 190
Cu(L3H)2 0.23 0.10 120
Supporting electrolyte ¼ 0.05 M n-Bu4NClO4, Solvent ¼ DMSO, aEpa ¼ Ligand based oxidation.
Reference electrode ¼ Ag/AgCl, Scan rate ¼ 100 mV s1.
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Figure 2. TGA curves of L1H2, L2H2 and L3H2 ligands.

3.1. NMR results

Although no chemical shifts were observed for ¼N–OH groups of oximes in the
1
H NMR spectra of L1H2, L2H2 and L3H2, the proton resonances support the
structures (table 4).
In the 1H NMR spectrum of L1H2, L2H2 and L3H2, the deuterium exchangeable NH
is a singlet at
¼ 5.2, 5.3 and 5.27 and 5.05, respectively (table 4).
In the 13C NMR spectrum of L1H2 the carbon resonances of oxime groups
are observed at 149.30 (C6) and 148.67 (C7) ppm and for L3H2 at (152.30) C6 and
(149.03 and 148.85) C7 ppm. For L3H2 (152.30) C6 (149.03 and 148.85) C7 ppm and
all other carbon resonances are double indicating that L3H2 has a cis–trans isomerism
[12]. The isomer ratio was found to be 64% cis-isomer and 36% trans-isomer from the
1
H NMR and 13C NMR data (table 4).
 Unsymmetrical vic-dioximes 867
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Figure 3. TGA curves of Co(L1H)2  2H2O, Co(L2H)2  2H2O and Co(L3H)2  2H2O.

Figure 4. TGA curves of Cu(L1H)2, Cu(L2H)2 and Cu(L3H)2.

3.2. IR results
In the IR spectrum of L1H2, L2H2 and L3H2 (as KBr pellets)  (OH) stretching
absorption is observed at 3540–2557, 3184 and 3351–3243 cm1, respectively.
 868 E. Tas et al.

The (N–H) stretching vibrations are at 3335 cm1 for L1H2, 3350 cm1 for L2H2
and 3388 cm1 for L3H2. The  (C¼N) and (N–O) vibrations are observed
at 1647–994 cm1 for L1H2, 1629–999 cm1 for L2H2 and 1645–994 cm1 for L3H2,
which are in agreement with values reported for vicinal dioxime derivatives [16].
The IR spectra of the complexes were characterized by the appearance of very
significant absorption band in the region 1724–1716 cm1 due to (O–H  O) [17]
and the shifts of (C¼N) absorptions to lower energy [18]. Downward shifts
(for L1H2, L2H2 and L3H2) of 34–6 cm1 for the (C¼N) absorption bands in the
Cu(II) and Co(II) complexes indicate coordination through the N atoms [19]. The
c(O–H) stretching band observed at 3540–2557, 3184 and 3351–3243 cm1 in
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the IR spectrum of L1H2, L2H2 and L3H2 together with the existence of an H-bridge
(O–H  O) near 1724–1716 cm1 and the shifting of (C¼N) and (N–O) stretching in
IR spectra of the Cu(II) and Co(II) complexes provide support for MN4-type
coordination in the complexes. IR data of the ligands and complexes are given
in table 2.

3.3. UV-VIS results

The UV-VIS spectra of the ligands (L1H2, L2H2 and L3H2) in CHCl3 and C2H5OH
showed three or four absorption bands between 244–311 nm for L1H2; three–five
absorption bands between 243–314 nm for L2H2 and four absorption bands between
247–343 nm for L3H2. Between 215–676 nm the Cu(II) and Co(II) complexes
in DMSO, CHCl3 and C2H5OH showed absorption bands. The absorptions in the
ultraviolet region are assignable to transitions involving ligands orbitals [20]. The
bands below 459 nm have very high extinction coefficients and are almost certainly
associated with intraligand  ! * and n ! * or charge–transfer transitions. In the
electronic spectra of the ligands and their metal complexes, the wide range of bands
seems to be due to  ! *, n ! * and d–d transitions and change-transfer transition
arising from  electron interactions between the metal and ligand, either metal-
to-ligand or ligand-to-metal electron transfer [21, 22]. The electronic spectra of
Cu(II) complexes in DMSO show a broad band at 550 nm for Cu(L1H)2, 676 nm for
Cu(L2H)2 and 670 nm for Cu(L3H)2 assigned to 2Eg ! 2T2g transitions, characteristic
for square-planar geometry [23]. Weak d–d metal absorption bands were observed at
634 nm for [Co(L1H)2  2H2O] in CHCl3, 697 nm for [Co(L2H)2  2H2O] in DMSO
and 536 nm for [Co(L3H)2  2H2O] in C2H5OH, respectively. Table 3 summarizes the
UV data for ligands and complexes.
The cobalt(II) and copper(II) complexes are paramagnetic. Their magnetic suscept-
ibilities are 3.39 BM for Co(L1H)2  2H2O, 3.69 BM for Co(L2H)2  2H2O, 3.76 BM
for Co(L3H)2  2H2O, 1.54 BM for Cu(L1H)2, 1.56 BM for Cu(L2H)2 and 1.58 BM
for Cu(L2H)2. The alternative chemical environments will give two (O–H  O)
bridge protons in the cis-form. According to the above results, a square-planar
geometry for the copper(II) complexes, and an octahedral geometry for the
cobalt(II) complex are proposed [24, 25]. The UV-VIS spectrum of the Co(II)
and Cu(II) complexes supports these structures because  ! * and d–d transitions
were observed, table 3. The suggested molecules of the complexes are shown in
figure 1.
 Unsymmetrical vic-dioximes 869

3.4. Thermogravimetric measurements

The thermal stability was investigated by TGA. The TGA curves, which were obtained
under nitrogen between 20–900
C show the cobalt(II) complexes to be thermally stable
to between 146
C with 339
C, whereas copper(II) complexes are thermally stable
between 179
C with 198
C. The ligand decomposition starts at 168
C for L1H2,
176
C L2H2, 105
C for L3H2 and are completed at 847oC for L2H2 and L3H2 and
769
C for L1H2. The Co(II) and Cu(II) complexes decompose in three steps in the
temperature ranges: 73–146, 146–324 and 324–495
C for Co(L1H)2  2H2O, 165–320,
320–508 and 508–560
C for Co(L2H)2  2H2O, 90–338, 338–462 and 462–671
C for
Co(L3H)2  2H2O with 147–179, 179–284 and 284–441
C for Cu(L1H)2, 139–193,
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193–292 and 292–393
C for Cu(L2H)2, 158–198, 198–295 and 295–433 for Cu(L3H)2.

3.5. Electrochemical studies

Redox properties of the Co(II) and Cu(II) complexes were studied by cyclic
voltammetry in dimethylsulfoxide (DMSO) containing 0.05 M tetra(n-butyl)ammonium
perchlorate, using a 2 mm sized Pt disc electrode. The electrochemical data are summar-
ized in table 5. The potentials are given versus Ag/AgCl reference electrode. The cyclic
voltammogram of Co(L1H)2 exhibits a reduction peak at Epc ¼ 1.50 V and an
associated re-oxidation peak at Epa ¼ 1.27 V. This redox couple is attributed to
Co(II)/Co(I) as shown in figure 5. The peak separation for this couple is

Ep ¼ 230 mV. The anodic peak potential shifted to more positive potentials and
the cathodic peak potential shifted to more negative potentials at higher scan rates.
Therefore, the separation in the peak potentials increased gradually at faster
scan rates. These data are indicative of a quasi-reversible one-electron redox process
corresponding to the Co(II)/Co(I) couple [26]. The ratio of Ip/v1/2 indicated that the
electrochemical process is diffusion controlled [26]. Co(L1H)2 also exhibits an irreversi-
ble oxidation peak at aEpa ¼ 0.19 V. This single oxidation peak may be attributed to the

60

50

40
I/mA

30

20
E(V) vs Ag/AgCl
10

0
-2 -1.5 -1 -0.5 0 0.5 1
-10

-20

-30

Figure 5. A cyclic voltammogram of 1.0  103 Co(L1H)2 in dimethylsulfoxide containing 0.05 M

n-Bu4NClO4. Scan rate: 100 mV s1. Reference electrode: Ag/AgCl.
 870 E. Tas et al.

100

80

I/mA
60

40
E(V) vs Ag/AgCl
20

-2 -1.5 -1 -0.5 00 0.5 1

Downloaded by [University of California Santa Cruz] at 20:23 11 October 2014

-20

-40

Figure 6. A cyclic voltammogram of 1.0  103 Co(L3H)2 in dimethylsulfoxide containing 0.05 M

n-Bu4NClO4. Scan rate: 100 mV s1. Reference electrode: Ag/AgCl.

2
I/mA

0
-0.4 -0.2 0 0.2 0.4 0.6 0.8 1

-1 E(V) vs Ag/AgCl

-2

Figure 7. A cyclic voltammogram of 5.0  104 M Cu(L1H)2 in dimethylsulfoxide containing 0.05 M

n-Bu4NClO4. Scan rate: 100 mV s1. Reference electrode: Ag/AgCl.

oxime of the ligand. In the reverse scan, no peaks are observed in the cathodic branch
indicating that the oxidation of the oxime moiety is irreversible. The peak potential
shifted to more positive potentials at faster scan rates, confirming the irreversibility
of the oxime-based oxidation. Figure 6 shows a cyclic voltammogram of Co(L3H)2.
As seen from table 5, the electrochemical properties of Co(L2H)2 and Co(L3H)2 are
similar, both undergoing one-electron reduction/oxidation assigned to Co(II)/Co(I)
couples. The separation in peak potentials clearly indicates that Co(L1H)2 has the
highest electron transfer rate. However, no irreversible oxidation peaks are observed
for Co(L2H)2 and Co(L3H)2 in the positive region. Figure 7 shows a cyclic voltammo-
gram of Cu(L1H)2. The voltammogram exhibits a redox couple whose reduction occurs
at Epc ¼ 0.16 V and oxidation at Epa ¼ 0.27 V assigned to quasi-reversible one electron
charge transfer of Cu(II)/Cu(I) couple with a single irreversible oxidation peak at
Epa ¼ 0.57 V. The separation in the peak potentials for Cu(II)/Cu(I) couple is
110 mV. Diagnostic tests for copper(II) complexes indicated that the electrochemical
 Unsymmetrical vic-dioximes 871

I/mA
1

0
-0.5 -0.2 0.1 0.4 0.7 1
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-1 E(V) vs Ag/AgCl

-2

Figure 8. A cyclic voltammogram of 5.0  104 Cu(L2H)2 in dimethylsulfoxide containing 0.05 M

n-Bu4NClO4. Scan rate: 100 mV s1. Reference electrode: Ag/AgCl.

behavior is also diffusion controlled. A cyclic voltammogram of Cu(L2H)2 is given in

figure 8. The reduction peak occurs at Epc ¼ 0.23 V with an associated reoxidation
peak at Epa ¼ 0.42 V. The separation in the peak potentials is 190 mV indicating a
quasi-reversible, one-electron process. No irreversible oxidation peaks were observed
at positive potentials for the other two copper(II) complexes. Data also revealed that
the electron transfer rate is higher for Cu(L1H)2 than the other two copper(II)
complexes. A general conclusion for electrochemical properties of metal complexes
is that all metal complexes show quasi-reversible one-electron redox processes.
However, Co(L1H)2 and Cu(L1H)2 complexes show another oxidation peak in the
positive region. This single irreversible oxidation peak is caused by the cyclic ring of
the ligand. Data also revealed that the electron transfer rates of metal complexes
with L1H2 are higher than the other metal complexes.

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