Transition Metal Chemistry
From 0.485 g of the respective chalcone. Yield 0.585 g,
75%; m.p. 159–160 °C. FTIR (KBr, cm−1): 3306, 3209 and
3156 (N–H), 3051 and 2942 ν(C–Hvinyl/C–Harom), 1593
ν(C=Cvinyl), 1519, 1482 and 1444 ν(C=N)+ ν(C=Carom),
140.6 (C9), 139.7, 139.4, 137.2, 133.6, 130.2 (C–Harom),
129.9 (2C–Harom), 129.7 (2C–Harom), 128.8 (2C–Harom),
128.6 (2C–Harom), 128.5 (2C–Harom), 127.3 (C–Harom),
125.8 (2C–Harom), 118.3 (C8), 21.5 (CH3). Minor isomer:
139.2, 139.1, 133.5, 130.5 (C–Harom), 130.0 (C–Harom),
129.6 (C–Harom), 128.7 (C–Harom), 127.9 (C–Harom), 125.7
(C–Harom), 21.4 (CH3). UV–Vis [CH3CN; λ/nm: 263, 340.
2-((E)-3-(4-Cyanophenyl)-1-phenylallylidene)-N-phenyl-
hydrazinecarbothioamide, HL4.
1
980 ν(C=Csubstituted trans), 771 ν(C=S). H NMR (DMSO-
d6): Major isomer: δ 11.54 (s, N2–H), 10.06 (s, N3–H),
7.89 (d, J = 16.10 Hz, H9), 7.84–7.14 (m, C–Harom), 6.84
(d, J = 16.10 Hz, H8). Minor isomer: 10.42 (s, N2–H),
9.03 (s, N3–H), 7.84–7.14 (m, C–Harom + H9), 6.49 (d,
J = 16.39 Hz, H8). 13C NMR (DMSO-d6): Major isomer:
177.2 (C=S), 148.9 (C=N), 139.4, 138.9 (C9), 137.0,
135.3, 134.3, 130.2 (2C–Harom), 129.9 (2C–Harom), 129.7
(C–Harom), 129.2 (2C–Harom), 128.8 (2C–Harom), 128.6
(2C–Harom), 125.9 (2C–Harom), 125.7 (C–Harom), 120.1 (C8).
Minor isomer: 139.2, 135.2, 133.7, 130.3, 129.8 (C–Harom),
129.4 (C–Harom), 129.1 (C–Harom), 128.7 (C–Harom), 125.5
(C–Harom) 125.3 (C–Harom). UV–Vis [CH3CN; λ/nm: 265,
343.
From 0.466 g of the respective chalcone. Yield 0.619 g,
81%; m.p. 176–177 °C. FTIR (KBr, cm−1): 3334, 3278
and 3213 ν(N–H), 3059, 2939 ν(C–Hvinyl/C–Harom),
2225 ν(C≡N), 1596 ν(C=Cvinyl), 1530, 1468 and 1439
ν(C=N)+ν(C=Carom), 973 ν(C=Csubstituted trans), 795 ν(C=S).
1H NMR (DMSO-d6): Major isomer: 10.46 (s, N2–H), 9.17
(s, N3–H), 7.99–7.19 (m, C–Harom), 7.47 (d, J=16.38 Hz,
H9), 6.56 (d, J = 16.38 Hz, H8). Minor isomer: δ 11.60
(s, N2–H), 10.10 (s, N3–H), 8.00 (d, J = 16.11 Hz, H9),
7.99–7.19 (m, C–Harom), 6.91 (d, J = 16.11 Hz, H8). 13C
NMR (DMSO-d6): Major isomer: 177.3 (C=S), 148.3
(C=N), 141.0, 139.4 (C-1′’’), 138.2 (C–Harom), 136.8,
132.9 (2C–Harom), 129.9 (2C–Harom), 129.8 (C–Harom),
129.1 (2C–Harom), 128.8 (C–Harom), 128.6 (2C–Harom), 126.0
(2C–Harom), 125.8 (C–Harom), 122.7 (C8), 119.3 (CN), 111.5.
Minor isomer: 140.9, 139.1, 135.1, 133.2 (C–Harom), 132.5,
130.3, 128.7 (C–Harom), 128.1 (C–Harom), 125.5 (C–Harom),
119.2 (CN), 111.1. UV–Vis [CH3CN; λ/nm: 266, 349.
2-((E)-3-(4-Nitrophenyl)-1-phenylallylidene)-N-phenyl-
hydrazinecarbothioamide, HL2.
From 0.506 g of the respective chalcone. Yield 0.660 g,
82%; m.p. 174–175 °C. FTIR (KBr, cm−1): 3332, 3276 and
3213 (N–H), 3060 and 2936 ν(C–Hvinyl/C–Harom), 1595
ν(C=Cvinyl), 1536, 1469 and 1441 ν(C=N)+ ν(C=Carom),
1340 (symmetrical N=O), 976 ν(C=Csubstituted trans), 789
1
ν(C=S). H NMR (DMSO-d6): Major isomer: δ 11.65 (s,
N2–H), 10.11 (s, N3–H), 8.29 (d, J = 8.91 Hz, 2Harom),
8.07–8.03 (m, C–Harom), 8.04 (d, J = 16.14 Hz, H9),
7.82–7.14 (m, C–Harom), 6.98 (d, J = 16.14 Hz, H8).
Minor isomer: 10.49 (s, N2–H), 9.19 (s, N3–H), 8.23 (d,
J=8.91 Hz, 2C–Harom), 8.07–8.03 (m, C–Harom), 7.82–7.14
(m, C–Harom + H9), 6.64 (d, J = 16.42 Hz, H8). 13C NMR
(DMSO-d6): Major isomer: 177.3 (C=S), 148.1 (C=N),
147.8, 143.0, 139.4, 137.7 (C9), 136.8, 129.9 (2C–Harom),
129.8 (C–Harom), 129.4 (2C–Harom), 128.8 (2C–Harom),
128.6 (2C–Harom), 126.0 (2C–Harom), 125.8 (C–Harom),
124.2 (2C–Harom), 123.5 (C8). Minor isomer: 177.3 (C=S),
147.3, 142.9, 139.1, 130.6 (C–Harom), 130.2 (C–Harom),
128.7 (C–Harom), 128.3 (C–Harom), 125.4 (C–Harom), 124.6
(2C–Harom). UV–Vis [CH3CN; λ/nm: 274, 370.
Synthesis of the complexes [Cu(L1–4)2] and [Zn(L1–
4)2]
Cu(II) and Zn(II) complexes were prepared from a general
procedure illustrated in Scheme 2. To a suspension of the
desired ligand HL1–HL4 (0.12 mmol) in 3 mL of metha-
nol was added Et3N (0.033 mL, 0.24 mmol), followed by
the addition of a previously prepared solution of the cor-
responding metal salt (0.010 g of CuCl2·2H2O or 0.008 g of
ZnCl2-0.06 mmol) in 2 mL of methanol. The resulting mix-
ture was stirred at room temperature for 2 h and centrifuged,
and the precipitate was washed with water and methanol and
dried. Crude products were purifed from diethyl ether by
crystallization and dried in open air.
2-((E)-3-(4-Tolyl)-1-phenylallylidene)-N-phenylhydrazi-
necarbothioamide, HL3.
From 0.444 g of the respective chalcone. Yield 0.505 g,
68%; m.p. 135–136 °C. FTIR (KBr, cm−1): 3308 and
3157 (N–H), 3049 ν(C–Hvinyl/C–Harom), 2950 and 2916
ν(C–Haliphatic), 1597 ν(C=Cvinyl), 1519, 1480 and 1444
ν(C=N)+ν(C=Carom), 981 ν(C=Csubstituted trans), 779 ν(C=S).
1H NMR (DMSO-d6): δ 11.48 (s, N2–H), 10.02 (s, N3–H),
7.86 (d, J = 16.07 Hz, H9), 7.73–7.14 (m, C–Harom), 6.80
(d, J=16.07 Hz, H8), 2.36 (s, CH3). Minor isomer: 10.39
(s, N2–H), 8.94 (s, N3-H), 7.73–7.14 (m, C–Harom + H9),
6.45 (d, J = 16.44 Hz, H8), 2.31 (s, CH3). 13C NMR
(DMSO-d6): Major isomer: 177.1 (C=S), 149.5 (C=N),
[Cu(L1)2], 1a. From 0.047 g of HL1. Yield 0.031 g,
61%; m.p. 140–142 °C. Anal. Calc. for C44H36Cl2N6S2Cu
· (CH3CH2)2O: C, 62.7; H, 4.8; N, 9.1%. Found: C, 63.2;
H, 5.0; N, 8.8%. FTIR (KBr, cm−1): 3406 (N–H); 3055 and
2924 ν(C–Hvinyl/C–Harom), 1597 ν(C=Cvinyl), 1526, 1495,
1475 and 1431 ν(C=N)+ν(C=Carom). UV–Vis [CH3CN; λ/
nm: 285, 323, 389.
[Cu(L2)2], 2a. From 0.048 g of HL2. Yield 0.040 g, 78%;
m.p. 134–135 °C. Anal. Calc. for C44H36N8O4S2Cu · 3/2
(CH3CH2)2O: C, 61.4; H, 5.1; N, 11.5. Found: C, 61.3; H,
5.2; N, 11.1%. FTIR (KBr, cm−1): 3336 and 3277 (N–H);
1 3