602
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
Maleev et al.
Lithium Λꢀbis[Nꢀsalicylideneꢀ(S)ꢀphenylalaninato]cobaltate
(m, 4 H, =CH2 of allyl); 7.11 (d, 2 H, Ar, J = 2.7 Hz); 7.52 (d, 2
H, Ar, J = 2.7 Hz); 8.47 (s, 2 H, CH=N).
(Li+[Λꢀ3]–). The yield was 11%, [α]D25 –3950 (с 0.032, MeOH).
Found (%): C, 62.05; H, 4.53; N, 4.41. C32H26N2O6CoLi•H2O.
Calculated (%): C, 62.15; H, 4.56; N, 4.53. 1H NMR (300 MHz,
D2O), δ: 3.26, 3.55 (both AB part of ABX system, 4 H, CH2ꢀPhe,
JAB = 13.7 Hz, JAX = 11.3 Hz, JBX = 3.6 Hz); 5.05 (X part of
ABX system, 2 H, αꢀHꢀPhe); 6.62 (d, 2 H, Ar, J = 8.5 Hz); 6.51
(t, 2 H, Ar, J = 8.5 Hz); 6.89 (ddd, 2 H, Ar, J = 8.5 Hz, J = 7.5 Hz,
J = 1 Hz); 7.0 (d, 2 H, Ar, J = 7.5 Hz); 7.24 (s, 2 H, CH=N);
7.38 (m, 10 H, Ph).
Lithium
Λ
ꢀ
bis[Nꢀ(3ꢀallylꢀ5ꢀbromosalicylidene)ꢀ(S)ꢀtryptoꢀ
phanato]cobaltate (Li+[
Λ
ꢀ6]–). The yield was 22%, [α]D25 –7330
(с 0.031, MeOH). Found (%): C, 53.12; H, 4.42; N, 5.96.
C42H34N4O6Br2CoLi•2 H2O. Calculated (%): C, 52.96; H, 4.02;
N, 5.88. 1H NMR (400 MHz, CD3OD), δ: 2.56, 2.61 (both AB
part of ABX system, 4 H, CH2 of allyl, JAB = 15.1 Hz, JAX = 6.4 Hz,
JBX = 8.0 Hz); 5.16 (X part of ABX system, 2 H, =CH of allyl);
3.55, 3.76 (both AB part of ABX system, 4 H, CH2ꢀTrp, JAB
=
Lithium Δꢀbis[Nꢀsalicylideneꢀ(S)ꢀphenylalaninato]cobaltate
(Li+[Δꢀ3]–). The yield was 66%, [α]D25 –4600 (с 0.030, MeOH).
Found (%): C, 62.21; H, 4.44; N, 4.56. C32H26N2O6CoLi•H2O.
Calculated (%): C, 62.15; H, 4.56; N, 4.53. 1H NMR (300 MHz,
D2O), δ: 3.32, 3.6 (both AB part of ABX system, 4 H, CH2ꢀPhe,
JAB = 13.8 Hz, JAX = 9.5 Hz, JBX = 3.7 Hz); 5.00 (X part of ABX
system, 2 H, αꢀH Phe); 6.57 (d, 2 H, Ar, J = 9.3 Hz); 6.62
(t, 2 H, Ar, J = 9.3 Hz); 6.82 (m, 2 H, Ar); 7.07 (d, 2 H, Ar,
J = 9.3 Hz); 7.11 (s, 2 H, CH=N); 7.40 (m, 10 H, Ph).
= 11.2 Hz, JAX = 4.4 Hz, JBX = 4.6 Hz); 4.95—5.07 (X part of
ABX system, 2 H, αꢀHꢀTrp); 4.54—4.68 (m, 4 H, =CH2 of
allyl); 6.63 (d, 2 H, Ar, J = 2.7 Hz); 6.68 (d, 2 H, Ar, J = 2.7 Hz);
7.13 (t, 2 H, Ar, J = 5.8 Hz); 7.16 (s, 2 H, CH=N); 7.18 (t, 2 H,
Ar, J = 5.6 Hz); 7.44 (d, 2 H, Ar, J = 6.3 Hz); 7.97 (d, 2 H, Ar,
J = 5.4 Hz).
Lithium
Δ
ꢀ
bis[Nꢀ(3ꢀallylꢀ5ꢀbromosalicylidene)ꢀ(S)ꢀtryptoꢀ
phanato
]
cobaltate (Li+[
Δ
ꢀ6]–). The yield was 70%, [α]D25 –7450
(с 0.030, MeOH). Found (%): C, 53.72; H, 3.42; N, 5.67.
C42H34N4O6Br2CoLi•H2O. Calculated (%): C, 53.98; H, 3.88;
N, 6.00. 1H NMR (400 MHz, CD3OD), δ: 3.16, 3.44 (both AB
part of ABX system, 4H, CH2 of allyl, JAB = 5.6 Hz, JAX = 7.2 Hz,
JBX = 5.8 Hz); 5.67 (X part of ABX system, 2 H, =CH of allyl);
Lithium Λꢀbis[Nꢀ(3ꢀallylꢀ5ꢀbromosalicylidene)ꢀ(S)ꢀvalinato]ꢀ
cobaltate (Li+[Λꢀ4]–). The yield was 30%, [α]D –3560
25
(с 0.035, MeOH). Found (%): C, 46.53; H, 4.64; N, 3.76.
C30H32N2O6Br2CoLi•2 H2O. Calculated (%): C, 46.30; H, 4.66;
N, 3.60. 1H NMR (300 MHz, CD3OD), δ: 1.2 (d, 6 H, CH3ꢀVal,
J = 2.1 Hz); 1.23 (d, 6 H, CH3ꢀVal, J = 2.1 Hz); 2.47—2.60
(m, 2 H, βꢀHꢀVal); 2.69—2.75 (m, 4 H, CH2 of allyl); 4.40
(d, 2 H, αꢀHꢀVal, J = 7.2 Hz); 4.78 (m, 4 H, =CH2 of allyl);
5.28—5.34 (m, 2 H, =CH of allyl); 6.81 (d, 2 H, Ar, J = 2.7 Hz);
7.39 (d, 2 H, Ar, J = 2.7 Hz); 8.35 (s, 2 H, CH=N).
3.59, 3.78 (both AB part of ABX system, 4 H, CH2ꢀTrp, JAB
=
= 14.4 Hz, JAX = 4.2 Hz, JBX = 4.6 Hz); 4.87 (X part of ABX
system, 2 H, αꢀHꢀTrp); 4.79—4.95 (m, 4 H, =CH2 of allyl); 6.65
(d, 2 H, Ar, J = 2.7 Hz); 6.83 (d, 2 H, Ar, J = 2.7 Hz); 7.05
(s, 2 H, CH=N); 7.12 (t, 2 H, Ar, J = 7.0 Hz); 7.24 (t, 2 H, Ar,
J = 6.9 Hz); 7.48 (d, 2 H, Ar, J = 8.4 Hz); 7.86 (d, 2 H, Ar,
J = 7.8 Hz).
Lithium Δꢀbis[Nꢀ(3ꢀallylꢀ5ꢀbromosalicylidene)ꢀ(S)ꢀvalinato]ꢀ
cobaltate (Li+[Δꢀ4]–). The yield was 53%, [α]D –4890
Lithium Λꢀbis[Nꢀ(3,5ꢀdichlorosalicylidene)ꢀ(S)ꢀvalinato]ꢀ
25
25
(с 0.030, MeOH). Found (%): C, 46.38; H, 4.84; N, 3.62.
C30H32N2O6Br2CoLi•2 H2O. Calculated (%): C, 46.30; H, 4.66;
N, 3.60. 1H NMR (300 MHz, CD3OD), δ: 1.16 (d, 6 H,
CH3ꢀVal, J = 6.9 Hz); 1.35 (d, 6 H, CH3ꢀVal, J = 6.9 Hz);
2.64—2.80 (m, 2 H, βꢀHꢀVal); 2.83, 3.12 (both AB part of ABX
system, 4 H, CH2 of allyl, JAB = 6.1 Hz, JAX = 3.8 Hz,
JBX = 5.5 Hz); 5.30 (X part of ABX system, 2 H, =CH of allyl);
4.33 (d, 2 H, αꢀHꢀVal, J = 3.6 Hz); 4.57—4.68 (m, 4 H, =CH2 of
allyl); 6.88 (d, 2 H, Ar, J = 2.7 Hz); 7.49 (d, 2 H, Ar, J = 2.7 Hz);
8.45 (s, 2 H, CH=N).
cobaltate (Li+[Λꢀ7]–). The yield was 22%, [α]D –2985
(с 0.035, MeOH). Found (%): C, 42.80; H, 3.44; N, 4.32.
C24H22N2O6Cl4CoLi•2 H2O. Calculated (%): C, 42.51; H, 3.86;
N, 4.13. 1H NMR (300 MHz, СD3OD), δ: 1.18 (d, 12 H,
CH3ꢀVal, J = 6.2 Hz); 2.46—2.55 (m, 2 H, βꢀHꢀVal); 4.42
(d, 2 H, αꢀHꢀVal, J = 7.0 Hz); 7.18 (d, 2 H, Ar, J = 2.7 Hz); 7.26
(d, 2 H, Ar, J = 3.0); 8.44 (s, 2 H, CH=N).
Lithium Δꢀbis[Nꢀ(3,5ꢀdichlorosalicylidene)ꢀ(S)ꢀvalinato]ꢀ
cobaltate (Li+[Δꢀ7]–). The yield was 70%, [α]D –2880
25
(с 0.035, MeOH). Found (%): C, 42.60; H, 3.77; N, 4.26.
C24H22N2O6Cl4CoLi•2 H2O. Calculated (%): C, 42.51; H, 3.86;
N, 4.13. 1H NMR (300 MHz, СD3OD), δ: 1.15 (d, 6 H,
CH3ꢀVal, J = 6.7 Hz); 1.30 (d, 6 H, CH3ꢀVal, J = 6.9 Hz);
2.70—2.80 (m, 2 H, βꢀHꢀVal); 4.26 (d, 2 H, αꢀHꢀVal, J = 8.4 Hz);
7.21 (d, 2 H, Ar, J = 2.7 Hz); 7.42 (d, 2 H, Ar, J = 3.0 Hz); 8.49
(s, 2 H, CH=N).
Lithium
Λ
ꢀ
bis[Nꢀ(3ꢀallylꢀ5ꢀbromosalicylidene)ꢀ(S)ꢀthreꢀ
oninato]cobaltate (Li+[
Λ
ꢀ5]–). The yield was 22%, [α]D25 –5350
(с 0.030, MeOH). Found (%): C, 43.19; H, 4.45; N, 3.78.
C28H28N2O8Br2CoLi•2 H2O. Calculated, (%): C, 42.99;
H, 4.12; N, 3.58. 1H NMR (400 MHz, CD3OD), δ: 1.42 (d, 6 H,
CH3ꢀThr, J = 6.1 Hz); 2.74, 2.76 (both AB part of ABX system,
4 H, CH2 of allyl, JAB = 14.1 Hz, JAX = 7.8 Hz, JBX = 7.7 Hz);
5.27 (X part of ABX system, 2 H, =CH of allyl); 4.04—4.17
(m, 2 H, βꢀHꢀThr); 4.54 (d, 2 H, αꢀHꢀThr, J = 7.6 Hz);
4.69—4.75 (m, 4 H, =CH2 of allyl); 6.81 (d, 2 H, Ar, J = 2.7 Hz);
7.41 (d, 2 H, Ar, J = 2.7 Hz); 8.32 (s, 2 H, CH=N).
Lithium Λꢀbis[Nꢀ(3ꢀmethoxysalicylidene)ꢀ(S)ꢀvalinato]coꢀ
baltate (Li+[Λꢀ8]–). The yield was 23%, [α]D
–3460
25
(с 0.031, MeOH). Found (%): C, 49.78; H, 5.93; N, 4.3.
C26H30N2O8CoLi•3.5 H2O. Calculated (%): C, 49.77; H, 5.94;
N, 4.46. 1H NMR (300 MHz, СD3OD), δ: 1.26—1.27 (m, 12 H,
CH3ꢀVal); 2.43—2.54 (m, 2 H, βꢀHꢀVal); 3.26 (s, 6 H, OMe);
4.47 (d, 2 H, αꢀHꢀVal, J = 7.3 Hz); 6.38 (t, 2 H, Ar, J = 7.8 Hz);
6.56 (d, 2 H, Ar, J = 7.6 Hz); 6.97 (d, 2 H, Ar, J = 7.8 Hz); 8.32
(s, 2 H, CH=N).
Lithium
Δ
ꢀ
bis[Nꢀ(3ꢀallylꢀ5ꢀbromosalicylidene)ꢀ(S)ꢀthreꢀ
oninato]cobaltate (Li+[
Δ
ꢀ5]–). The yield was 65%, [α]D25 –6120
(с 0.031, MeOH). Found (%): C, 43.07; H, 4.21; N, 3.64.
C28H28N2O8Br2CoLi•2 H2O. Calculated (%): C, 42.99; H, 4.12;
N, 3.58. 1H NMR (400 MHz, CD3OD), δ: 1.44 (d, 6 H,
CH3ꢀThr, J = 6.4 Hz); 2.83, 3.09 (both AB part of ABX system,
4 H, CH2 of allyl, JAB = 12.4 Hz, JAX = 6.8 Hz, JBX = 6.4 Hz);
5.46 (X part of ABX system, 2 H, =CH of allyl); 4.51—4.67
(m, 2 H, βꢀHꢀThr); 4.64 (d, 2 H, αꢀHꢀThr, J = 8.4 Hz); 4.70—4.83
Lithium Δꢀbis[Nꢀ(3ꢀmethoxysalicylidene)ꢀ(S)ꢀvalinato]coꢀ
baltate (Li+[Δꢀ8]–). The yield was 65%, [α]D
–6980
25
(с 0.034, MeOH). Found (%): C, 54.10; H, 5.54; N, 4.92.
C26H30N2O8CoLi•H2O. Calculated (%): C, 53.62; H, 5.54;
N, 4.81. 1H NMR (300 MHz, СD3OD), δ: 1.18—1.28 (m, 12 H,