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Beloglazkina et al.
1H NMR (CDCl3), δ: 8.77 (s, 2 H); 8.47 (m, 4 H); 7.92 (d, 2 H,
J = 7.3 Hz); 7.78 (d, 2 H, J = 7.6 Hz); 7.50 (d, 2 H, J = 8.1 Hz);
7.35 (m, 6 H).
2,2´ꢀ[Ethaneꢀ1,2ꢀdiylbis(thio)]bis[Nꢀ(3ꢀpyridyl)benzaldꢀ
imine] (5). Compound 2 (906 mg, 3 mmol) and 3ꢀaminopyridine
(564 mg, 6 mmol) were dissolved in EtOH (15 mL). The reacꢀ
tion mixture was refluxed for 15 h and filtered. The solvent was
distilled off. A brown oil was obtained in a yield of 1 g (73%).
1H NMR (CDCl3), δ: 8.99 and 9.00 (both s, 2 H); 8.46 (m, 4 H);
8.12 (d, 2 H, J = 7.7 Hz); 7.47 (d, 2 H, J = 7.9 Hz); 7.30
(m, 8 H); 3.07 and 3.03 (both d, 4 H, J = 2.5 Hz).
General procedure B. A solution of the corresponding metal
salt (0.02 mmol) in EtOH (1 mL) was slowly added along the
wall of the vessel to a solution of ligand 4—9 (0.02 mmol) in
CHCl3 (1 mL) in such a way as to obtain a twoꢀphase system.
The vessel with the reaction mixture was tightly closed and kept
until crystals formed. The precipitate was filtered off, washed
with Et2O, and dried in air.
Tetrachloro{bis[2ꢀ(3ꢀpyridyliminomethyl)phenyl]disulfide}diꢀ
copper(II) (10) was synthesized according to the method A.
The yield was 70%. Found (%): C, 42.57; H, 3.90;
N, 8.20. C26H24Cl4Cu2N4OS2. Calculated (%): C, 42.11;
H, 3.24; N, 7.56.
{2,2´ꢀ[Ethaneꢀ1,2ꢀdiylbis(thio)]bis[Nꢀ(3ꢀpyridyl)benzaldꢀ
imine]}nickel(II) diperchlorate (11) was synthesized according to
the method B. The yield was 34%. Found (%): C, 39.30; H, 3.90;
N, 7.05. C26H30Cl2N4NiO12S2. Calculated (%): C, 39.80;
H, 3.83; N, 7.14.
2,2´ꢀ[Propaneꢀ1,3ꢀdiylbis(thio)]bis[Nꢀ(3ꢀpyridyl)benzaldꢀ
imine] (6). Compound 3 (948 mg, 3 mmol) and 3ꢀaminopyridine
(564 mg, 6 mmol) were dissolved in EtOH (15 mL). The reacꢀ
tion mixture was refluxed for 15 h and filtered. The solvent was
distilled off. A brown oil was obtained in a yield of 980 mg
1
(70%). H NMR (CDCl3), δ: 9.02 and 9.01 (both s, 2 H); 8.49
(m, 4 H); 8.12 and 7.50 (both m, 2 H each); 7.34 (m, 8 H); 3.03
and 3.02 (both t, 4 H, J = 7.0 Hz); 1.93 (m, 2 H). MS,
m/z (Irel (%)): 467 [M – H]+ (2.5), 161 (57.0), 149 (43.0), 137
(100.0), 109 (79.7).
Dichloro{2,2´ꢀ[ethaneꢀ1,2ꢀdiylbis(thio)]bis[Nꢀ(3ꢀpyriꢀ
dyl)benzaldimine]}dinickel(II) (12) was synthesized according
to the method B. The yield was 83%. Found (%): C, 43.73;
H, 3.96; N, 7.81. C28H28Cl4N4Ni2OS2. Calculated (%):
C, 44.21; H, 3.68; N, 7.37.
{2,2´ꢀ[Ethaneꢀ1,2ꢀdiylbis(thio)]bis[Nꢀ(3ꢀpyridyl)benzaldꢀ
imine]}cobalt(II) diperchlorate (13) was synthesized according to
the method B. The yield was 65%. Found (%): C, 39.10; H, 3.35;
N, 7.57. C26H30Cl2CoN4O12S2. Calculated (%): C, 39.80;
H, 3.83; N, 7.14.
Dichloro{2,2´ꢀ[ethaneꢀ1,2ꢀdiylbis(thio)]bis[Nꢀ(3ꢀpyriꢀ
dyl)benzaldimine]}cobalt(II) (14) was synthesized according
to the method B. The yield was 65%. Found (%): C, 50.30;
H, 3.84; N, 9.21. C26H26Cl2N4NiO2S2. Calculated (%):
C, 50.32; H, 4.19; N, 9.03.
{2,2´ꢀ[Propaneꢀ1,3ꢀdiylbis(thio)]bis[Nꢀ(3ꢀpyridyl)benzaldꢀ
imine]}copper(II) diperchlorate (15) was synthesized according
to the method B. The yield was 92%. Found (%): C, 44.48;
H, 3.50; N, 7.81. C27H24Cl2CuN4O8S2. Calculated (%):
C, 44.35; H, 3.29; N, 7.67.
{2,2´ꢀ[Propaneꢀ1,3ꢀdiylbis(thio)]bis[Nꢀ(3ꢀpyridyl)benzaldꢀ
imine]}copper(II) diperchlorate (16) was synthesized according
to the method B. The yield was 56%. Found (%): C, 44.69;
H, 3.53; N, 8.01. C29H30Cl4Cu2N4OS2. Calculated (%):
C, 44.44; H, 3.83; N, 7.15.
Dichloro{2,2´ꢀ[propaneꢀ1,3ꢀdiylbis(thioꢀ2,1ꢀphenylene)]ꢀ
bis(1,3ꢀbenzothiazole)}copper(II) (17) was synthesized according
to the method A. The yield was 85%. Found (%): C, 52.16;
H, 3.92; N, 4.32. C29H26Cl2CuN2S4. Calculated (%): C, 52.37;
H, 3.91; N, 4.21.
Bis[2ꢀ(2ꢀbenzothiazolyl)phenyl] disulfide (7). A mixture of
2,2´ꢀdithiobenzaldehyde (1) (274 mg, 1 mmol) and 2ꢀaminoꢀ
thiophenol (0.216 mL, 250 mg, 2 mmol) was refluxed in EtOH
(15 mL) in the presence of glacial acetic acid (0.5 mL) for 15 h.
The precipitate that formed was filtered off and dried in air.
A paleꢀyellow powder was obtained in a yield of 404 mg (84%),
m.p. 202 °C. Found (%): C, 64.55; H, 3.35; N, 5.70. C26H16N2S4.
Calculated (%): C, 64.46; H, 3.31; N, 5.79. 1H NMR (CDCl3),
δ: 8.17 and 7.97 (both d, 2 H each, J = 7.9 Hz); 7.93 (dd, 2 H,
J1 = 0.9 Hz, J2 = 7.9 Hz); 7.87 (dd, 2 H, J1 = 1.3 Hz, J2 =
7.7 Hz); 7.55 (dt, 2 H, J1 = 1.1 Hz, J2 = 7.6 Hz); 7.46 (dt, 2 H,
J1 = 1.1 Hz, J2 = 7.5 Hz); 7.39 (dt, 2 H, J1 = 1.5 Hz, J2 =
7.2 Hz); 7.33 (dt, 2 H, J1 = 1.3 Hz, J2 = 7.5 Hz).
2,2´ꢀ[Ethaneꢀ1,2ꢀdiylbis(thioꢀ2,1ꢀphenylene)]bis(1,3ꢀbenzoꢀ
thiazole) (8). Compound 2 (604 mg, 2 mmol) and 2ꢀaminoꢀ
thiophenol (0.431 mL, 500 mg, 4 mmol) were refluxed in EtOH
(15 mL) in the presence of glacial acetic acid (0.5 mL) for 15 h.
The precipitate that formed was filtered off and dried in air.
A yellow powder was obtained in a yield of 715 mg (70%), m.p.
128 °C. Found (%): C, 65.50; H, 3.70; N, 5.40. C28H20N2S4.
Calculated (%): C, 65.36; H, 3.91; N, 5.47. 1H NMR (CDCl3),
δ: 8.13 (d, 2 H, J = 8.0 Hz); 7.99 (dd, 2 H, J1 = 1.8 Hz, J2 =
8.1 Hz); 7.93 (d, 2 H, J = 8.0 Hz); 7.53 (t, 2 H, J = 7.4 Hz); 7.40
(m, 8 H); 3.10 (s, 4 H).
2,2´ꢀ[Propaneꢀ1,3ꢀdiylbis(thioꢀ2,1ꢀphenylene)]bis(1,3ꢀbenꢀ
zothiazole) (9). Compound 3 (316 mg, 1 mmol) and 2ꢀaminoꢀ
thiophenol (0.216 mL, 250 mg, 2 mmol) were refluxed in EtOH
(15 mL) in the presence of glacial acetic acid (0.5 mL) for 15 h.
The reaction solution was passed through a silica gel filter colꢀ
umn (h = 3 cm), and the solvent was distilled off. A brown oil
{2,2´ꢀ[Propaneꢀ1,3ꢀdiylbis(thioꢀ2,1ꢀphenylene)]bis(1,3ꢀbenꢀ
zothiazole)}copper(II) diperchlorate (18) A. The yield was 85%.
Found (%): C, 43.99; H, 2.91; N, 3.72. C29H26Cl2CuN2S4.
Calculated (%): C, 43.88; H, 2.77; N, 3.79.
1
was obtained in a yield of 0.28 g (52%). H NMR (CDCl3), δ:
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ
00584ꢀa).
8.13 (d, 2 H, J = 8.0 Hz); 7.99 (dd, 2 H, J1 = 1.8 Hz, J2 =
8.1 Hz); 7.93 (d, 2 H, J = 8.0 Hz); 7.53 (t, 2 H, J = 7.4 Hz); 7.40
(m, 8 H); 3.10 (s, 4 H).
Synthesis of the complexes (general procedure A). A solution
of the corresponding metal salt (0.02 mmol) in EtOH (1 mL)
was added to a solution of ligand 4—9 (0.02 mmol) in EtOH
(3—4 mL). The reaction mixture was refluxed for 15 h and then
cooled to –18 °C. The precipitate was filtered off, washed with
Et2O, and dried in air.
References
1. S. V. Kryatov, B. S. Mohanraj, V. V. Tarasov, O. P. Kryatova,
E. V. RybakꢀAkimova, B. Nithakki, J. F. Rusling, R. J.
Staples, and A. Y. Nazarenko, Inorg. Chem., 2002, 41, 923.