Synthesis and electrochemistry of (5Z,5′Z)-2,2′-(alkane- α,ω-diyldisulfanyldiyl)-bis(5-(2-pyridylmethylene)-3, 5-dihydro-4H-imidazol-4-one) complexes with cobalt(II) chloride

Article abstract of DOI:10.1007/s11172-006-0092-7

A series of S-alkylated 2-thiohydantoin derivatives containing two 5-(2-pyridylmethylene)-2-sulfanyl-3,5-dihydro-4H-imidazol-4-one moieties linked through a polymethylene bridge with different numbers of carbon atoms was synthesized for the first time. Th

Full text of DOI:10.1007/s11172-006-0092-7

Russian Chemical Bulletin, International Edition, Vol. 54, No. 9, pp. 2163—2168, September, 2005
2163
Synthesis and electrochemistry of (5Z,5´Z )ꢀ2,2´ꢀ(alkaneꢀα,ωꢀ
diyldisulfanyldiyl)ꢀbis(5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ
4Hꢀimidazolꢀ4ꢀone) complexes with cobalt(II) chloride*
E. K. Beloglazkina,ꢀ A. G. Majouga, I. V. Yudin, N. V. Zyk, A. A. Moiseeva, and K. P. Butin†
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Eꢀmail: bel@org.chem.msu.su
A series of Sꢀalkylated 2ꢀthiohydantoin derivatives containing two 5ꢀ(2ꢀpyridylmethylene)ꢀ
2ꢀsulfanylꢀ3,5ꢀdihydroꢀ4Нꢀimidazolꢀ4ꢀone moieties linked through a polymethylene bridge
with different numbers of carbon atoms was synthesized for the first time. These compounds
were obtained by the alkylation of 3ꢀphenylꢀ5ꢀ(2ꢀpyridylmethylene)ꢀ2ꢀthiohydantoin or
3ꢀmethylꢀ5ꢀ(2ꢀpyridylmethylene)ꢀ2ꢀthiohydantoin with different α,ωꢀdibromoalkanes in acꢀ
etone or DMF in the presence of potassium carbonate. Complexes of these compounds (L)
with CoCl2 were synthesized. In all cases, the complexes L(CоCl2)2 were formed regardless of
the ratio of L and inorganic salt introduced into the reaction. According to electronic spectroꢀ
scopic data, the cobalt atom in the complexes has a tetrahedral coordination environment. The
synthesized ligands and complexes were electrochemically studied by cyclic voltammetry.
Key words: (5Z,5´Z )ꢀ2,2´ꢀ(alkaneꢀα,ωꢀdiyldisulfanyldiyl)bis(5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀ
dihydroꢀ4Нꢀimidazolꢀ4ꢀones, complexes with cobalt(II) chloride, electronic absorption specꢀ
troscopy, cyclic voltammetry.
2ꢀThiohydantoins (4ꢀoxoimidazolidineꢀ2ꢀthiones)
and their Sꢀalkylated derivatives (2ꢀalkylthioꢀ3,5ꢀdihydroꢀ
4Hꢀimidazolꢀ4ꢀones) attract researchers´ attention in the
recent time as convenient synthetic intermediates conꢀ
taining both electrophilic and nucleophilic carbon atoms
and due to a wide spectrum of their biological activity.1—3
We reported4 the synthesis and structural and physiꢀ
cochemical studies of the complexes of (5Z )ꢀ2ꢀmethylꢀ
thioꢀ3ꢀphenylꢀ5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Нꢀ
imidazolꢀ4ꢀone and 3ꢀmethylꢀ(5Z )ꢀ2ꢀmethylthioꢀ5ꢀ
(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Нꢀimidazolꢀ4ꢀone
with NiII, CoII, and CuII salts.
The present work describes the synthesis and physicoꢀ
chemical study of derivatives of Sꢀalkylated analogs of
2ꢀthiohydantoins containing two 5ꢀ(2ꢀpyridylmethylene)ꢀ
2ꢀsulfanylꢀ3,5ꢀdihydroꢀ4Нꢀimidazolꢀ4ꢀone moieties
linked through a polymethylene bridge. Their complexꢀ
ation with CoII chloride was also studied.
toin (2), which were synthesized from phenyl or methyl
isothiocyanate, glycine, and 2ꢀpyridinecarbaldehyde acꢀ
cording to described procedures,5 were chosen as the startꢀ
ing compounds for the syntheses of the target ligands.
Ligands 3—9 were prepared by the alkylation of the thione
group of compounds 1 and 2 with different α,ωꢀdibromoꢀ
alkanes. Two procedures were used for the alkylation.
According to the first procedure (method A), the alkylaꢀ
tion was carried out in acetone in the presence of potasꢀ
sium carbonate and a catalytic amount of triethylbenzylꢀ
ammonium chloride as the phaseꢀtransfer catalyst.6 Acꢀ
cording to the second procedure (method B), the alkylaꢀ
tion was carried out in DMF in the presence of the same
base (Scheme 1).
As found for the reactions of 3ꢀphenylꢀ5ꢀ(2ꢀpyridylꢀ
methylene)ꢀ2ꢀthiohydantoin (1) with α,ωꢀdibromoalkaꢀ
nes, the yields of the target products are virtually the same
for both alkylation methods. In the case of thiohydanꢀ
toin 2, only method B was used. The yields of the reaction
products, viz., ligands L, are given in Table 1.
Synthesis of ligands
The compositions of the compounds synthesized were
confirmed by the elemental analysis data, and their strucꢀ
3ꢀPhenylꢀ5ꢀ(2ꢀpyridylmethylene)ꢀ2ꢀthiohydantoin
(1) and 3ꢀmethylꢀ5ꢀ(2ꢀpyridylmethylene)ꢀ2ꢀthiohydanꢀ
1
tures were determined by the data of Н and 13C NMR
1
and IR spectroscopies. In the Н NMR spectra of comꢀ
pounds 3—9, the signal from the NH groups disappears,
while it is present in the spectra of the corresponding
thiohydantoins 1 and 2, and a signal of protons of CH2S
* Dedicated to Academician N. S. Zefirov on the occasion of his
70th birthday.
† Deceased.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2099—2104, September, 2005.
1066ꢀ5285/05/5409ꢀ2163 © 2005 Springer Science+Business Media, Inc.

2164
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Beloglazkina et al.
Scheme 1
Table 1. Yields of compounds 3—9 prepared by methods А and В
Starting
5ꢀ(2ꢀpyriꢀ
dylmethylene)ꢀ
2ꢀthiohydantoin
Starting
α,ωꢀdibromoꢀ
alkane
Proꢀ Yield of product
duct
(%)
A
B
1
2
1,2ꢀDibromoethane
1,6ꢀDibromohexane
1,8ꢀDibromooctane
1,10ꢀDibromodecane 6
1,4ꢀDibromobutane
1,6ꢀDibromohexane
3
4
5
—
64
62
67
—
—
—
73
68
—
73
67
71
69
7
8
1,10ꢀDibromodecane 9
due to which powdered precipitates of the complexes were
formed.
It has previously been shown4,17 that the reactions of
the (5Z)ꢀ2ꢀmethylthioꢀ3ꢀphenyl(or 3ꢀmethyl)ꢀ5ꢀ(2ꢀpyriꢀ
dylmethylene)ꢀ3,5ꢀdihydroꢀ4Нꢀimidazolꢀ4ꢀone ligands
with CoII and CuII chlorides afford complexes LMCl2, in
which the metal ion has a tetrahedral ligand environment
and coordinates to two nitrogen atoms (of the pyridine
and imidazole moieties) and two chloride anions. Each of
the ligands studied in the present work (L) has two
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Нꢀimidazolꢀ4ꢀone
moieties. Therefore, we can expect а priori that they would
form 1 : 1 (LCoCl2) or 1 : 2 [L(CoCl2)2] complexes in the
reactions with cobalt chloride. However, the 1 : 2 comꢀ
plexes [L(CoCl2)2] were isolated in all cases, regardless of
the ratio of ligand L and inorganic salt introduced into
complexation. The compositions of the resulting comꢀ
pounds were determined from the elemental analysis data.
All the complexes are green and poorly soluble in DMF
and DMSO and do not melt at temperatures below 300 °C.
The data on the composition of the complexes are given
in Table 2.
R = Ph (1, 3—6), Me (2, 7—9)
n = 2 (3), 4 (7), 6 (4, 8), 8 (5), 10 (6, 9)
Reagents and conditions: i. Method A: K2CO3, acetone,
Et3BnNCl, 20 °C; ii. Method B: K2CO3, DMF, 20 °C.
at 3.2 ppm appears. The IR spectra of the compounds
synthesized exhibit an absorption band of the C=N group
at 1670 cm–1
.
Synthesis of complexes
According to published data, 2ꢀthiohydantoins and
their Sꢀalkylated derivatives with transition metal salts
form complexes in which the metal ion can coordinate to
the nitrogen or sulfur atom, or simultaneously to both of
these atoms.8—15
To obtain the target complexes, we used the method
of slow diffusion of a solution of ligand L (3, 5—7) in
CH2Cl2 into an alcoholic solution of CoCl2•6H2O,5,7,16
Complexes 3a, 5a, 6a, and 7a were characterized by
the data of electronic and IR spectroscopies. The IR specꢀ
tra of all the complexes contain the shift of the absorption
band of the C=O group of the ligand toward higher freꢀ
Table 2. Composition, yield, and elemental analysis data for complexes 3a and 5a—7a
Ligand
Complex
Composition
of complex
Yield
(%)
Found
Calculated
Molecular
formula
(%)
C
Н
N
3
5
6
7
3а
5а
6а
7а
3•2CoCl2
65
74
80
68
44.96
45.30
46.07
46.26
48.15
48.21
36.30
36.57
2.76
2.85
4.26
4.29
4.34
4.45
3.53
3.58
9.59
9.91
8.52
8.52
8.22
8.43
10.45
10.66
C32H24Cl4Co2N6O2S2
C38H42Cl4Co2N6O5S2
C40H44Cl4Co2N6O4S2
C24H28Cl4Co2N6O4S2
5•2CoCl2•3H2O
6•2CoCl2•2H2O
7•2CoCl2•2H2O

CoII Complexes of Sꢀalkylated thiohydantoins
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2165
A
Table 3. Data of electronic absorption spectroscopy in the UV
and visible regions for CоCl2•6H2O, ligands 5—7, and comꢀ
plexes 3а and 5а—7а (CH3CN, C = 4•10–3 mol L–1
)
1
0.8
Compound
λ/nm (logε)
0.6
2
CoCl2•6H2O
214 (3.9), 255 (3.6), 570 (3.5), 613 (2.5),
678 (2.7)
0.4
5
272 (4.79), 364 (5.08)
0.2
6
271 (4.69), 361 (4.97)
7
275 (4.85), 364 (5.15)
3а
5а
6а
7а
262(3.81), 372(3.78), 552 (3.25), 634 (3.38)
276 (3.74), 380 (3.97), 560 (3.05), 660 (3.09)
259 (3.77), 379 (3.65), 584 (2.91), 675 (3.00)
279 (3.56), 380 (3.84), 555 (1.96), 634 (2.15)
1600
1650
1700
1750
cm–1
Fig. 1. IR spectra (Nujol) at 1550—1750 cm–1 of ligand 7 (1)
and its complex with CoCl2 7а (2).
A (rel. units)
quencies compared to those of the starting compounds
(Fig. 1). On the contrary, the vibrational frequencies of
the C=N and C=C bonds decrease.
1.2
1.0
0.8
0.6
0.4
0.2
The electronic absorption spectra of ligands 5—7 conꢀ
tain absorption bands only in the UV region correspondꢀ
ing to the π–π*ꢀ and n—π*ꢀtransitions. For the starting
CoCl2•6H2O in which the metal ion has an octahedral
ligand environment, the spectrum exhibits three mediumꢀ
intensity bands of the d—dꢀtransitions in the visible reꢀ
gion (500—700 nm). When complexation occurs, the inꢀ
tensity of the absorption bands of the ligand in the UV
region decreases and the bands of the d—dꢀtransitions of
the metal shift along with the simultaneous decrease in
their intensity (Table 3 and Fig. 2), which is usually obꢀ
served when the geometry of the complex changes from
octahedral to tetrahedral. The electronic absorption specꢀ
tra suggest that the coordination environment of the metal
in the complexes under study is similar to that in similar
mononuclear cobalt complexes containing (5Z )ꢀ(2ꢀpyriꢀ
dylmethylene)ꢀ3,5ꢀdihydroꢀ4Нꢀimidazolꢀ4ꢀone4 as a
ligand. Thus, according to the data of elemental analysis
and spectroscopy, we ascribe the following structures to
all of the complexes synthesized.
3
1
2
500
600
700
800 λ/nm
Fig. 2. Electronic absorption spectra of ligand 7 (1), complex
7a (2), and CoCl2•6H2O (3) in the visible region (CH3CN, C =
4•10–3 mol L–1).
supporting electrolyte at a glassyꢀcarbon (GC) disk elecꢀ
trode by the methods of cyclic voltammetry (CV) and
rotating disk electrode (RDE).
2
10 µA
3
1
n = 2, 4, 6, 8, 10
1
0
–1
–2
E/V
Electrochemical studies
Fig. 3. Cyclic voltammograms (200 mV s–1) in a DMF/0.05 М
Bu4NClO4 solution of ligand 3 (C = 10–3 mol L–1) (1), beforeꢀ
hand synthesized complex 3a (C = 10–3 mol L–1) (2), and a
mixture of ligand 3 (C = 10–3 mol L–1) and CoCl2•6H2O (C =
2•10–3 mol L–1) 5 min after mixing (3).
The behavior of compounds 3 and 5—7 and their comꢀ
plexes (Table 4, Fig. 3) was electrochemically studied in
DMF solutions in the presence of 0.05 М Bu4NClO4 as a

2166
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Beloglazkina et al.
Table 4. Electrochemical potentials of reduction (Ered) and oxiꢀ
dation (Eox) of the ligands and their complexes measured by
the CV (Ep is the peak potential) and RDE methods (E1/2 is the
halfꢀwave potential) at the GC electrode in DMF/0.05 M
different ligands) after the reactants were mixed, after
which it stops changing.
The typical CV curves of the ligand, isolated complex,
and a ligand—CoCl2 mixture obtained 5 min after disꢀ
solution are presented in Fig. 3 for ligand 3 and its
complex 3а. It is seen that the voltammogram of a
ligand—transition metal salt mixture corresponds comꢀ
pletely to that for the complex synthesized beforehand.
We observed a similar pattern for all other systems under
study. Thus, the electrochemical method provides preꢀ
liminary information on a possibility of synthesis of cheꢀ
late complexes with ligands of this type in a chosen solꢀ
vent and on the complexation rate.
The first reduction peak of the complexes under study
corresponds to the twoꢀelectron process (which was proved
by the electrochemical study on the RDE as compared to
the wave of the oneꢀelectron oxidation of ferrocene).
This means that two cobalt atoms are independent of
each other, i.e., the reduction of the first metal cenꢀ
ter (CoII → CoI) has no effect on the second cobalt
atom, which is reduced, therefore, at the same potential
(about –0.7 V). Probably, this is related to the fact that
one coordinated cobalt atom is considerably remote from
another atom and the donating nitrogen atoms are not
connected by any conjugated system of bonds via which
electrons could be transferred.
Bu4NClO4 (CV 200 mV s–1, RDE 20 mV s–1, 2800 min–1
)
red
red
ox
ox
Comꢀ
pound
Ер
Е1/2
Ер
Е1/2
V
3
–1.20
–1.82
–2.18
–0.67
–1.19
–1.74
–2.22
–1.25
–1.17*
–1.90
–0.72
–1.20
–1.78
–2.20
–1.35
–1.88
–0.71
–0.59*
–1.24
–2.16
–1.20
–1.10
–1.74*
–2.12
–0.68
–0.97
–1.70
–2.22
–1.18 (2е)
–1.90 (1е)
–2.26 (1е)
–0 .64 (2e)
–1.05 (2e)
–1.48
1.56 1.54 (1.7е)
1.28 1.24 (2e)
3а
–1.95
5
–1.22 (2е)
–1.95 (1е)
–2.21
–0.65 (2е)
–1.08 (2е)
–1.44
1.52 1.48 (2е)
–2.35 (1е)
1.26 1.20 (2е)
5a
–2.00
6
–1.18 (2е)
–1.83 (2е)
–0.66 (2е)
–0.94
–1.40
–1.90
1.60 1.62 (2е)
1.26 1.20 (2е)
6а**
7
–1.14 (1е)
–1.82 (1е)
1.60 1.58 (2е)
1.30 1.34 (2е)
Experimental
The starting compounds 1 and 2 were synthesized from pheꢀ
nyl isothiocyanate (or methyl isothiocyanate), glycine, and
2ꢀpyridinecarbaldehyde according to earlier described proceꢀ
dures.5 The course of the reactions was monitored by TLC on
Silufol plates.
7а
–0.62 (1е)
–1.44
1Н and 13C NMR spectra were measured on a Varianꢀ
XRꢀ400 instrument with a working frequency of 400 and
100 MHz, respectively, in CDCl3. IR spectra were recorded on
an URꢀ20 instrument in Nujol and on an IRꢀ200 FTIR specꢀ
CoCl2•6H2O –0.86 (1е) –1.30 (2е)
1.53 1.50 (1е)
1.70 1.70 (1е)
–1.21 (1е)
0.35
Note. The number of electrons transferred in this step and deterꢀ
mined using the RDE method by a comparison with the wave of
oneꢀelectron oxidation of ferrocene.
* Peak potentials in inverse scans of the CV curves.
** Low solubility.
trometer (ThermoNicolet, USA) with a resolution of 4 cm–1
.
UV spectra were recorded on a Perkin—Elmer, λꢀ25 instruꢀ
ment in CH3CN. Mass spectra were obtained on a Finnigan
MAT 95 XL instrument (ionization energy 70 eV, temperature
of the source 200 °C, temperatureꢀprogrammed regime of the
rod 30—290 °C/15 deg min–1). Oxidation and reduction potenꢀ
tials were measured on a PIꢀ50ꢀ1.1 potentiostat connected with
a PRꢀ8 programmer. Cyclic voltammograms and waves on the
RDE were recorded on a twoꢀcoordinate recorder. The workꢀ
ing electrode was a glassyꢀcarbon disk electrode. Potentials
were measured relative to the standard potential of the ferꢀ
rocene/ferrocenium ion (Fc/Fc+) redox system using a silver
chloride Ag/AgCl/KCl(sat.) reference electrode. The supporting
electrolyte was tetrabutylammonium perchlorate (C4H9)4NClO4
(highest purity grade (99.8%), Fluka).
The complexes of ligands 3 and 5—7 with cobalt chloꢀ
ride are reduced much more easily than the correspondꢀ
ing ligands. All the complexes under study are stable and
do not dissociate in DMF to the free ligand and CoCl2. In
addition, the complexes are formed rather rapidly from
the corresponding ligands and CoCl2•6H2O, which are
taken in stoichiometric and comparatively low concenꢀ
trations (10–3 mol L–1), directly in an electrochemical
cell. In 2—3 min, the CV curve of the mixture exhibits the
appearance of a new peak in the nearꢀcathodic region
(–0.60 V). This peak is absent from the CV of the starting
substrates, and its intensity increases for 5—10 min (for
Reactions of 3ꢀphenylꢀ2ꢀthioxoꢀ5((Z )ꢀ2ꢀpyridylmethylꢀ
ene)imidazolꢀ4ꢀone (1) and 3ꢀmethylꢀ2ꢀthioxoꢀ5((Z )ꢀ2ꢀpyridylꢀ
methylene)imidazolꢀ4ꢀone (2) with α,ωꢀdibromoalkanes (general
procedure). A. α,ωꢀDibromoalkane (2.5 mmol) was added for

CoII Complexes of Sꢀalkylated thiohydantoins
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2167
5 min with stirring to a mixture of compound 1 (1.4 g, 5 mmol),
dry K2CO3 (1.04 g, 7.5 mmol), and a catalytic amount of
triethylbenzylammonium chloride (0.57 g, 0.25 mmol) in acꢀ
etone (10—15 mL). The reaction mixture was stirred for 1 h
at ~20 °C, and a precipitate that formed was filtered off and
washed with acetone. The filtrate was evaporated in vacuo to
dryness, and a precipitate that formed was recrystallized from
ethyl acetate.
B. α,ωꢀDibromoalkane (2.5 mmol) was added for 5 min
with stirring at –10 °C to a mixture of compound 1 (1.4 g,
5 mmol) or compound 2 (1.1 g, 5 mmol) and dry K2CO3 (1.04 g,
7.5 mmol) in DMF (15 mL). The reaction mixture was stirred
for 2 h at –10 °C and then for 2 h at room temperature. Then
water (50 mL) was added to the mixture. A precipitate that
formed was filtered off, washed with water, and recrystallized
from ethyl acetate.
(5Z,5´Z )ꢀ2,2´ꢀ(Ethaneꢀ1,2ꢀdiyldisulfanyldiyl)bis(3ꢀphenylꢀ
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone) (3),
m.p. 259 °C. 1Н NMR, δ: 8.75 (d, 1 H, HαꢀPy, J = 7.9 Hz); 8.66
(d, 1 H, Hβ´ꢀPy, J = 4.0 Hz); 7.81 (td, 1 H, HβꢀPy, J1 = 7.3 Hz,
J2 = 2.3 Hz); 7.42 (m, 3 H, Ph); 7.29 (m, 2 H, Ph); 7.11 (td,
1 H, HγꢀPy, J1 = 7.5 Hz, J2 = 1.0 Hz); 7.18 (s, 1 H, CH=); 3.11
(t, 2 H, SCH2, J = 7.5 Hz). 13C NMR, δ: 169.43, 166.77,
154.33, 150.96, 140.46, 136.86, 132.76, 130.43, 129.07, 128.02,
125.61, 124.14, 108.10, 30.22. IR, ν/cm–1: 1710 (C=O); 1670
(C=N); 1640 (C=C). Mass spectrum, m/z (Irel (%)): 588 [М]+
(2). Found (%): C, 65.28; H, 4.10; N, 14.11. C32H24N6S2O2.
Calculated (%): C, 65.31; H, 4.08; N, 14.29.
(5Z,5´Z )ꢀ2,2´ꢀ(Butaneꢀ1,4ꢀdiyldisulfanyldiyl)bis(3ꢀmethylꢀ
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone) (7),
m.p. 220 °C. 1H NMR, δ: 8.82 (d, 1 H, HαꢀPy, J = 7.9 Hz); 8.59
(d, 1 H, Hβ´ꢀPy, J = 4.0 Hz); 7.71 (td, 1 H, HβꢀPy, J1 = 7.3 Hz,
J2 = 2.3 Hz); 7.38 (m, 3 H, Ph); 7.31 (m, 2 H, Ph); 7.23 (s, 1 H,
CH=); 7.13 (dd, 1 H, HγꢀPy, J1 = 7.5 Hz, J2 = 0.9 Hz); 3.41 (t,
2 H, SCH2, J = 7.5 Hz); 3.08 (s, 3 H, NMe); 2.19 (quint, 2 H,
CH2, J = 7.5 Hz). IR, ν/cm–1: 1700 (C=O); 1660 (C=N); 1600
(C=C). Mass spectrum, m/z (Irel (%)): 492 [М]+ (13).
(5Z,5´Z )ꢀ2,2´ꢀ(Hexaneꢀ1,6ꢀdiyldisulfanyldiyl)bis(3ꢀmethylꢀ
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone) (8),
m.p. 205 °C. 1H NMR, δ: 8.74 (d, 1 H, HαꢀPy, J = 7.9 Hz); 8.63
(d, 1 H, Hβ´ꢀPy, J = 3.9 Hz); 7.69 (td, 1 H, HβꢀPy, J1 = 7.3 Hz,
J2 = 2.3 Hz); 7.35 (m, 3 H, Ph); 7.29 (m, 2 H, Ph); 7.17 (s, 1 H,
CH=); 7.11 (dd, 1 H, HγꢀPy, J1 = 7.5 Hz, J2 = 1.0 Hz); 3.34 (t,
2 H, SCH2, J = 7.4 Hz); 3.07 (s, 3 H, NMe); 1.91 (quint, 2 H,
CH2, J = 7.5 Hz); 1.59 (quint, 2 H, CH2, J = 7.5 Hz). 13C NMR,
δ: 170.60, 168.20, 154.70, 150.8, 141.34, 136.64, 127.62, 124.02,
123.68, 30.64, 29.05, 28.49, 26.71. IR, ν/cm–1: 1700 (C=O);
1670 (C=N); 1610 (C=C). Mass spectrum, m/z (Irel (%)):
524 [М]+ (6).
(5Z,5´Z )ꢀ2,2´ꢀ(Decaneꢀ1,10ꢀdiyldisulfanyldiyl)bis(3ꢀmethylꢀ
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone) (9),
m.p. 191 °C. 1H NMR, δ: 8.81 (d, 1 H, HαꢀPy, J = 7.9 Hz); 8.67
(d, 1 H, Hβ´ꢀPy, J = 3.9 Hz); 7.71 (td, 1 H, HβꢀPy, J1 = 7.3 Hz,
J2 = 2.3 Hz); 7.41 (m, 3 H, Ph); 7.29 (m, 2 H, Ph); 7.21 (s, 1 H,
CH=); 7.10 (dd, 1 H, HγꢀPy, J1 = 7.5 Hz, J2 = 0.9 Hz); 3.37 (t,
2 H, SCH2, J = 7.4 Hz); 3.18 (s, 3 H, NMe); 1.86 (quint, 2 H,
CH2, J = 7.3 Hz); 1.46 (m, 4 H, CH2—CH2). 13C NMR, δ:
184.2, 166.2, 150.9, 143.7, 143.0, 136.8, 128.2, 123.6, 106.0,
42.8, 39.5, 29.6, 29.15, 29.0. IR, ν/cm–1: 1700 (C=O);
1670 (C=N); 1600 (C=C). Mass spectrum, m/z (Irel (%)):
580 [М]+ (13).
Synthesis of complexes (general procedure). Ethanol (3 mL)
was carefully (over the flask wall) added to a solution of ligand 3
or 5—7 (0.034 mmol) in CH2Cl2 (2—3 mL) in such a manꢀ
ner that a twoꢀphase system was formed. Then a solution
of CoCl2•6H2O (16 mg, 0.068 mmol) in EtOH (2—3 mL)
was slowly added. The flask with the reaction mixture was
tightly closed and kept until a precipitate was formed. The preꢀ
cipitate was filtered off and dried in air. (5Z,5´Z )ꢀ2,2´ꢀ(Ethaneꢀ
1,2ꢀdiyldisulfanyldiyl)bis(3ꢀphenylꢀ5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀ
dihydroꢀ4Нꢀimidazolꢀ4ꢀone)dinickel(II) tetrachloride (3а),
(5Z,5´Z )ꢀ2,2´ꢀ(octaneꢀ1,8ꢀdiyldisulfanyldiyl)bis(3ꢀphenylꢀ
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Нꢀimidazolꢀ4ꢀone)diꢀ
nickel(II) tetrachloride trihydrate (5а), (5Z,5´Z )ꢀ2,2´ꢀ(decaneꢀ
1,10ꢀdiyldisulfanyldiyl)bis(3ꢀphenylꢀ5ꢀ(2ꢀpyridylmethylene)ꢀ
3,5ꢀdihydroꢀ4Нꢀimidazolꢀ4ꢀone)dinickel(II) tetrachloride diꢀ
hydrate (6а), and (5Z,5´Z )ꢀ2,2´ꢀ(butaneꢀ1,4ꢀdiyldisulfanylꢀ
diyl)bis(3ꢀmethylꢀ5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Нꢀimidꢀ
azolꢀ4ꢀone)dinickel(II) tetrachloride dihydrate (7а) were thus obꢀ
tained.
(5Z,5´Z )ꢀ2,2´ꢀ(Hexaneꢀ1,6ꢀdiyldisulfanyldiyl)bis(3ꢀphenylꢀ
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone) (4),
m.p. 240 °C. 1H NMR, δ: 8.77 (d, 1 H, HαꢀPy, J = 7.9 Hz); 8.66
(d, 1 H, Hβ´ꢀPy, J = 3.9 Hz); 7.75 (td, 1 H, HβꢀPy, J1 = 7.3 Hz,
J2 = 2.3 Hz); 7.45 (m, 3 H, Ph); 7.30 (m, 2 H, Ph); 7.17 (s, 1 H,
CH=); 7.13 (dd, 1 H, HγꢀPy, J1 = 7.5 Hz, J2 = 0.9 Hz); 3.32 (t,
2 H, SCH2, J = 7.5 Hz); 1.86 (quint, 2 H, CH2, J = 7.6 Hz);
1.54 (quint, 2 H, CH2, J = 7.5 Hz). 13C NMR, δ: 153.86,
150.04, 135.94, 132.22, 129.50, 129.20, 127.28, 126.76, 124.05,
123.12, 52.03, 50.05, 38.47, 30.89, 28.80, 28.40. IR, ν/cm–1
:
1700 (C=O); 1670 (C=N); 1630 (C=C). Found (%): C, 66.71;
H, 5.04; N, 12.65. C36H32N6S2O2. Calculated (%): C, 67.06;
H, 5.00; N, 13.03.
(5Z,5´Z )ꢀ2,2´ꢀ(Octaneꢀ1,8ꢀdiyldisulfanyldiyl)bis(3ꢀphenylꢀ
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone) (5),
m.p. 242 °C. 1H NMR, δ: 8.77 (d, 1 H, HαꢀPy, J = 7.9 Hz); 8.65
(d, 1 H, Hβ , J = 3.9 Hz); 7.73 (td, 1 H, HβꢀPy, J1 = 7.3 Hz,
´ꢀPy
J2 = 2.3 Hz); 7.45 (m, 3 H, Ph); 7.30 (m, 2 H, Ph); 7.17 (s, 1 H,
CH=); 7.15 (dd, 1 H, HγꢀPy, J1 = 7.5 Hz, J2 = 0.9 Hz); 7.19 (s,
1 H, CH=); 1.82 (quint, 2 H, SCH2, J = 14.1 Hz); 1.64 (m, 2 H,
CH2); 1.42 (m, 4 H, CH2—CH2). IR, ν/cm–1: 1680 (C=O);
1660 (C=N); 1610 (C=C). Mass spectrum, m/z (Irel (%)):
672 [М]+ (13).
(5Z,5´Z )ꢀ2,2´ꢀ(Decaneꢀ1,10ꢀdiyldisulfanyldiyl)bis(3ꢀphenylꢀ
5ꢀ(2ꢀpyridylmethylene)ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone) (6),
m.p. 243 °C. 1H NMR, δ: 8.83 (d, 1 H, HαꢀPy, J = 7.9 Hz); 8.69
(d, 1 H, Hβ´ꢀPy, J = 3.9 Hz); 7.77 (td, 1 H, HβꢀPy, J1 = 7.3 Hz,
J2 = 2.3 Hz); 7.40 (m, 3 H, Ph); 7.30 (m, 2 H, Ph); 7.20 (s, 1 H,
CH=); 7.13 (dd, 1 H, HγꢀPy, J1 = 7.5 Hz, J2 = 0.9 Hz); 3.32 (t,
2 H, CH2, J = 7.3 Hz); 1.42 (m, 2 H, CH2); 1.24 (m, 6 H,
(CH2)6). IR, ν/cm–1: 1690 (C=O); 1670 (C=N); 1600 (C=C).
Found (%): C, 68.23; H, 5.95; N, 11.67. C40H40N6O2S2. Calcuꢀ
lated (%): C, 68.54; H, 5.75; N, 11.09.
The data on the composition of the complexes and the yields
of the compounds synthesized are presented in Tables 1 and 2.
Their spectral data are given in Table 3.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 04ꢀ03ꢀ32845)
and the Foundation "Universities of Russia" (Grant
05.03.046).

2168
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Beloglazkina et al.
10. M. Choudhry, A. Burrows, M. Mingos, J. White, and
D. Williams, Chem. Commun., 1995, 1521.
References
11. M. Chowdhry, M. Mingos, A. White, and D. Williams, Chem.
Commun., 1996, 899.
1. US Pat. 3994904; Chem. Abstr., 1976, 86, 10658m.
2. Czech. Pat. 151744; Chem. Abstr., 1974, 81, 63633b.
3. US Pat. 4452798A; Chem. Abstr., 1985, 101, 38476b.
4. A. G. Majouga, Ph. D. (Chem.) Thesis, M. V. Lomonosov
Moscow State University, Moscow, 2005, 137 pp. (in
Russian).
5. V. Zubenko, Tr. L´vov. Med. Inꢀta [Works of Lvov Medical
Institute], 1957, 12, 83 (in Russian); Chem. Abstr., 1960, 54,
21059h.
6. K. KiecꢀKononowicz and J. KarolakꢀWojciechowska, Phosꢀ
phorus, Sulfur, Silicon, 1992, 73, 235.
7. J. Casas, E. Castellano, A. Macfas, N. Playa, A. Sanchez,
J. Sordo, and J. ZukermanꢀSchpector, Inorg. Chim. Acta,
1995, 238, 129.
12. J. Casas, A. Castineiras, N. Playa, A. Sanchez, J. Sordo,
J. Varela, and E. VazquezꢀLopez, Polyhedron, 1999, 18, 3653.
13. J. Casas, E. Castellano, A. Masias, N. Playa, A. Sanchez,
J. Sordo, J. Varela, and E. VazquezꢀLopez, Polyhedron, 2001,
20, 1845.
14. P. Molina, A. Tarrada, D. Curiel, and C. Ramirez
de Arellano, Tetrahedron, 1999, 55, 1417.
15. M. Arca, F. Demartin, F. Devillanova, A. Garau, F. Isaia,
V. Lippolis, and G. Verani, Inorg. Chem., 1998, 37, 4164.
16. A. Hassaan, Sulfur Lett., 1991, 13, 1.
17. A. G. Majouga, E. K. Beloglazkina, S. Z. Vatsadze, A. A.
Moiseeva, K. P. Butin, and N. V. Zyk, Mendeleev Commun.,
2004, 14, 115.
8. R. S. Srivastаva, R. R. Srivastava, and H. N. Bhargava, Soc.
Chim. Fr., 1991, 128, 671.
9. D. Kushev, G. Gorneva, V. Enchev, E. Naydenova,
J. Popova, S. Taxirov, L. Maneva, K. Grancharov, and
N. Spassovska, J. Inorg. Biochem., 2002, 89, 203.
Received February 28, 2005;
in revised form June 21, 2005