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Belokon´ et al.
J = 13.2 Hz); 7.09 (d, 2 H, CHAr, J = 8.1 Hz); 7.43 (d, 2 H,
CHAr, J = 11.7 Hz); 8.40 (s, 2 H, CH=N).
7.43—7.50 (m, 10 H, CHAr); 7.60 (d, 2 H, CHAr, J = 6.4 Hz);
7.90 (d, 2 H, CH=N, J = 6.4 Hz); 10.39 (s, 2 H).
Potassium Λꢀbis[Nꢀsalicylideneꢀ(S)ꢀphenylalaninato]coꢀ
baltate (2d). The yield was 79%, m.p. >300 °C, [α]D –3793.6
Potassium Λꢀbis[Nꢀ3,5ꢀdiꢀtertꢀbutylsalicylideneꢀ(S)ꢀtryptoꢀ
phanato]cobaltate (2l). The yield was 76%, m.p. 190—192 °C,
[α]D25 –726.7 (c 0.0030, MeOH). Found (%): C, 67.21; H, 7.01;
N, 5.38. C52H60CoKN4O6. Calculated (%): C, 66.79; H, 6.47;
N, 5.99. 1H NMR (200 MHz, D2O + CD3COCD3 (1 : 1)), δ:
1.42 (d, 36 H, Me, J = 16.0 Hz); 3.50 (m, 4 H, CH); 3.14 (t,
2 H, J = 14.0 Hz); 3.41 (d, 2 H, J = 11.4); 4.83 (d, 2 H, СH, J =
8.4 Hz); 6.03 (d, 2 H, CHAr, J = 8.0 Hz); 6.15 (s, 2 H, CHAr);
6.50 (d, 2 H, CHAr, J = 9.0 Hz); 6.68, 6.90, 6.97 (all s, 2 H each,
CHAr); 7.26 (d, 2 H, CHAr, J = 7.4 Hz); 7.44 (d, 2 H, CHAr, J =
7.2 Hz); 7.66 (d, 2 H, CH=N, J = 7.0 Hz).
25
(c 0.0031, MeOH). Found (%): C, 60.41; H, 4.31; N, 4.29.
C32H26CoKN2O6. Calculated (%): C, 60.76; H, 4.14; N, 4.43.
1H NMR (300 MHz, D2O + CD3COCD3 (1 : 1)), δ: 3.30 (s,
2 H, CH); 3.50 (d, 2 H, CH, J = 7.2 Hz); 4.71 (s, 2 H, CH); 6.36
(t, 2 H, CHAr, J = 9.0 Hz); 6.80 (t, 4 H, CHAr, J = 8.1 Hz); 7.13
(t, 2 H, CHAr, J = 9.3 Hz); 7.20 (s, 2 H, CHAr); 7.45 (m, 8 H,
CHAr); 7.54 (s, 2 H, CH=N).
Potassium Λꢀbis[Nꢀsalicylideneꢀ(S)ꢀasparaginato]cobaltate
(2g). The yield was 80%, m.p. >300 °C, [α]D25 –0.004 (c 0.0032,
MeOH). Found (%): C, 39.81; H, 3.61; N, 8.79.
C22H20CoKN4O8•5H2O. Calculated (%): C, 40.25; H, 4.61;
Potassium
Λꢀbis[Nꢀ5ꢀbromosalicylideneꢀ(S)ꢀtryptoꢀ
phanato]cobaltate (2m). The yield was 69%, m.p. >300 °C,
[α]D25 –3280.0 (c 0.0030, MeOH). Found (%): C, 46.97; H, 3.40;
N, 5.87. C36H26Br2CoKN4O6•3H2O. Calculated (%): C, 46.87;
H, 3.50; N, 6.07. 1H NMR (300 MHz, D2O + CD3COCD3
(1 : 1)), δ: 3.52 (t, 2 H, CH, J = 10.8); 3.75 (d, 2 H, CH, J =
15.2 Hz); 4.64 (s, 6 H, H2O); 4.86 (d, 2 H, CH, J = 12.0 Hz);
6.36 (d, 2 H, CHAr, J = 9.0 Hz); 6.84 (m, 4 H, CHAr); 7.05 (m,
8 H, CHAr); 7.44 (d, 2 H, CHAr, J = 7.8 Hz); 7.82 (d, 2 H,
CH=N, J = 7.8 Hz).
Exchange of counterions (general procedure). Complex 1b
or 2h (100 mg) was dissolved in a mixture of H2O and EtOH
(5 mL each) and passed through the DOWEXꢀ50x8 ionꢀexꢀ
change resin containing ions of the corresponding metals as
counterions. The resulting solution was concentrated, and the
residue was purified by gel chromatography on Sephadex LHꢀ20
using an EtOH—benzene (1 : 3) mixture as the eluent.
Silver ∆ꢀbis[Nꢀsalicylideneꢀ(S)ꢀvalinato]cobaltate (1n).
M.p. >300 °C. Found (%): C, 46.25; H, 4.53; N, 4.49.
C24H26AgCoN2O6•H2O. Calculated (%): C, 46.24; H, 4.40;
N, 4.23. 1H NMR (300 MHz, D2O), δ: 1.29 (m, 12 H, Me); 2.55
(m, 2 H, CH); 4.20 (br.s, 2 H, CH2); 4.50 (s, 2 H, H2O); 6.50
(br.s, 4 H, CHAr); 6.97 (br.s, 2 H, CHAr); 7.40 (br.s, 2 H,
CHAr); 8.40 (br.s, 2 H, CH=N).
Lithium Λꢀbis[Nꢀsalicylideneꢀ(S)ꢀtryptophanato]cobaltate
(2o). M.p. >300 °C, [α]D25 –5346 (c 0.0030, MeOH). Found (%):
C, 59.41; H, 4.34; N, 7.44. C36H28CoLiN4O6•2.5H2O. Calcuꢀ
lated (%): C, 59.76; H, 4.60; N, 7.74. 1H NMR (200 MHz,
D2O + CD3COCD3 (1 : 1)), δ: 3.09, 3.50 (both s, 2 H each,
CH); 4.54 (s, 5 H, H2O); 4.90 (d, 2 H, CH, J = 11.2 Hz); 6.17
(m, 2 H, CHAr); 6.32 (m, 4 H, CHAr); 6.50 (d, 2 H, CHAr, J =
7.4 Hz); 6.90 (s, 2 H, CHAr); 7.17 (m, 4 H, CHAr); 7.41 (s, 2 H,
CHAr); 7.60 (d, 2 H, CHAr, J = 7.4 Hz); 7.90 (d, 2 H, CH=N,
J = 7.8 Hz).
1
N, 8.53. H NMR (300 MHz, D2O), δ: 3.00 (d, 4 H, CH2, J =
9.8 Hz); 4.65 (s, 10 H, H2O); 5.29 (t, 2 H, CH, J = 12.2 Hz);
6.30 (d, 2 H, CHAr, J = 11.0 Hz); 6.64 (t, 2 H, CHAr, J =
12.2 Hz); 6.90 (t, 2 H, CHAr, J = 12.3 Hz); 7.40 (d, 2 H, CHAr
J = 12.3 Hz); 8.40 (s, 2 H, CH=N).
,
Potassium Λꢀbis[Nꢀsalicylideneꢀ(S)ꢀtryptophanato]cobaltate
25
(2h). The yield was 86%, m.p. >300 °C, [α]D –4062.5,
[α]57825 –3737.5, [α]54625 –737.5 (c 0.0032, MeOH). Found (%):
C, 61.53; H, 4.74; N, 7.57. C36H28CoKN4O6•Et2O. Calcuꢀ
lated (%): C, 61.22; H, 4.88; N, 7.14. 1H NMR (200 MHz,
D2O + CD3COCD3 (1 : 1)), δ: 1.13 (t, 3 H, Me (Et2O)); 3.14 (t,
2 H, CH, J = 14.0 Hz); 3.41 (d, 2 H, CH, J = 11.4 Hz); 3.50 (q,
2 H, CH2 (Et2O)); 4.83 (d, 2 H, CH, J = 8.4 Hz); 6.03 (d, 2 H,
CHAr, J = 8.0 Hz); 6.15 (s, 2 H, CHAr); 6.50 (d, 2 H, CHAr, J =
9.0 Hz); 6.68 (s, 2 H, CHAr); 6.90 (s, 2 H, CHAr); 6.97 (s, 4 H,
CHAr); 7.26 (d, 2 H, CHAr, J = 7.4 Hz); 7.43 (d, 2 H, CHAr, J =
7.2 Hz); 7.83 (d, 2 H, CH=N, J = 7.0 Hz).
Potassium
Λꢀbis[Nꢀ3ꢀmethoxysalicylideneꢀ(S)ꢀtryptoꢀ
phanato]cobaltate (2i). The yield was 89%, m.p. >300 °C,
[α]D25 –4613.3 (c 0.0030, MeOH). Found (%): C, 55.07; H, 4.67;
N, 5.73. C38H32CoKN4O8•3H2O. Calculated (%): C, 55.34;
H, 4.64; N, 6.79. 1H NMR (300 MHz, D2O + CD3COCD3
(1 : 1)), δ: 2.90 (s, 6 H, OMe); 3.60, 4.00 (both s, 2 H each,
CH); 4.65 (s, 6 H, H2O); 5.00 (br.s, 2 H, CH); 6.20 (s, 4 H,
CHAr); 6.50, 6.90 (both s, 2 H each, CHAr); 7.20 (s, 4 H, CHAr);
7.30 (s, 2 H, CHAr); 7.50 (d, 2 H, CHAr, J = 7.8 Hz); 8.00 (br.s,
2 H, CH=N).
Potassium
Λꢀbis[Nꢀ4ꢀhydroxysalicylideneꢀ(S)ꢀtryptoꢀ
phanato]cobaltate (2j). The yield was 76%, m.p. >300 °C,
[α]D25 –3967.7 (c 0.0031, MeOH). Found (%): C, 52.19; H, 4.89;
N, 6.17. C36H26CoK3N4O8•0.5H2O. Calculated (%): C, 52.23;
H, 3.29; N, 6.77. 1H NMR (300 MHz, D2O + CD3COCD3
(1 : 1)), δ: 3.34 (t, 2 H, CH, J = 12.0 Hz); 3.60 (d, 2 H, CH, J =
12.0 Hz); 4.12 (s, 1 H, H2O); 5.00 (d, 2 H, CH, J = 9.3 Hz);
5.70 (s, 2 H, CHAr); 5.80 (d, 2 H, CHAr, J = 7.5 Hz); 6.40 (d,
2 H, CHAr, J = 7.8 Hz); 6.70 (s, 2 H, CHAr); 7.10 (m, 6 H,
CHAr); 7.50 (d, 2 H, CHAr, J = 6.9 Hz); 7.80 (d, 2 H, CH=N,
J = 6.9 Hz).
Potassium Λꢀbis[Nꢀ4ꢀbenzyloxysalicylideneꢀ(S)ꢀtryptoꢀ
phanato]cobaltate (2k). The yield was 70%, m.p. 207—209 °C,
[α]D25 –2969.7 (c 0.0033, MeOH). Found (%): C, 59.71; H, 5.07;
N, 5.19. C50H40CoKN4O8. Calculated (%): C, 60.36; H, 5.25;
N, 5.61. 1H NMR (400 MHz, CDCl3), δ: 3.43 (t, 2 H, CH, J =
12.0 Hz); 3.86 (d, 2 H, CH, J = 12.4 Hz); 4.94 (d, 2 H, CH, J =
8.8 Hz); 6.00 (d, 2 H, CHAr, J = 8.8 Hz); 6.20 (s, 2 H, CHAr);
6.72 (d, 2 H, CHAr, J = 8.4 Hz); 7.26—7.42 (m, 8 H, CHAr);
Sodium Λꢀbis[Nꢀsalicylideneꢀ(S)ꢀtryptophanato]cobaltate
25
(2p). M.p. >300 °C, [α]D –4856.2 (c 0.0029, MeOH).
Found (%): C, 59.62; H, 5.21; N. 6.90. C36H28CoN4NaO6•
•2H2O. Calculated (%): C, 59.18; H, 4.41; N, 7.67. 1H NMR
(300 MHz, D2O + CD3COCD3 (1 : 1)), δ: 3.00, 3.58 (both s,
2 H each, CH); 4.57 (s, 4 H, H2O); 4.81 (d, 2 H, CH, J =
12.0 Hz); 6.17 (m, 4 H, CHAr); 6.50 (d, 2 H, CHAr, J = 7.2 Hz);
6.68, 6.90 (both s, 2 H each, CHAr); 7.10 (m, 4 H, CHAr); 7.41
(s, 2 H, CHAr); 7.53 (d, 2 H, CHAr, J = 7.8 Hz); 7.95 (d, 2 H,
CH=N, J = 7.5 Hz).
Cesium Λꢀbis[Nꢀsalicylideneꢀ(S)ꢀtryptophanato]cobaltate
25
25
(2q). M.p. >300 °C, [α]D
–3142.0, [α]578 –2838.7,
[α]54625 –509.7 (c 0.0031, MeOH). Found (%): C, 54.38; H, 4.31;
N, 6.78. C36H28CoCsN4O6. Calculated (%): C, 53.75; H, 3.51;