1896
D.A. Safin et al. / Inorganica Chimica Acta 362 (2009) 1895–1900
Table 2
Selected bond lengths (Å), and bond angles (°) for 3
H
H
N
O
O
P
S
R N
Bond lengths
Cu(1)–S(1)
Cu(1)–S(2)
Cu(1)–P(2)
S(1)–P(1)
2.2679(8)
2.2231(8)
2.2161(7)
1.9974(9)
1.753(3)
P(1)–O(1)
P(1)–O(2)
P(1)–N(1)
N(1)–C(1)
N(2)–C(1)
1.5878(19)
1.5871(18)
1.617(2)
1.315(3)
1.371(4)
S
R:
S(2)–C(1)
N
N
H2N
N
HLc
Bond angles
HLa
HLb
S(1)–Cu(1)–S(2)
S(1)–Cu(1)–P(2)
S(2)–Cu(1)–P(2)
Cu(1)–S(1)–P(1)
Cu(1)–S(2)–C(1)
S(1)–P(1)–O(1)
S(1)–P(1)–O(2)
S(1)–P(1)–N(1)
O(1)–P(1)–O(2)
114.12(3)
124.90(3)
120.98(3)
92.13(3)
105.29(10)
109.89(8)
113.83(18)
117.50(8)
100.16(10)
O(1)–P(1)–N(1)
O(2)–P(1)–N(1)
N(1)–C(1)–N(2)
P(1)–N(1)–C(1)
S(2)–C(1)–N(1)
P(1)–N(1)–C(1)
S(2)–C(1)–N(1)
S(2)–C(1)–N(2)
N(1)–C(1)–N(2)
106.99(11)
106.89(11)
120.0(2)
124.58(18)
128.9(2)
129.1(3)
128.4(3)
113.9(3)
117.6(3)
Chart 1.
concentrated until the crystallization began. The residue was
recrystallized from a dichloromethane to n-hexane mixture 1:5
(v/v). Complexes were obtained as colorless crystals (see Tables 1
and 2).
2.1.1. Cu(PPh3)2La ꢁ CH2Cl2 (1)
N3O2P3S2 (1005.45): C, 58.53; H, 5.11; N, 4.18. Found: C, 58.64;
H, 5.05; N, 4.24%.
Yield: 1.820 g (66%). M.p. 137 °C. 1H NMR (CDCl3): d = 1.30 (d,
3JH,H = 6.3 Hz, 6H, CH3), 1.32 (d, JH,H = 6.3 Hz, 6 H, CH3), 4.75 (d,
3
3
3
sept, JPOCH = 11.0 Hz, JH,H = 6.1 Hz, 2H, OCH), 6.91 (ddd,
2.1.2. Cu(PPh3)2Lb (2)
3JH5,H4 = 7.2 Hz, JH6,H5 = 4.9 Hz, JH5,H3 = 1.0 Hz, 1H, C5H, Py),
3
4
Yield: 2.291 g (83%). M.p. 132 °C. 1H NMR (CDCl3): d = 1.27 (d,
3
3
7.27–7.46 (m, 30H, 2PPh3), 7.58 (ddd, JH4,H3 = 8.5 Hz, JH5,H4
=
3
3JH,H = 6.2 Hz, 6H, CH3), 1.29 (d, JH,H = 6.2 Hz, 6H, CH3), 4.71 (d,
4
3
7.1 Hz, JH6,H4 = 1.7 Hz, 1H, C4H, Py), 8.23 (dd, JH6,H5 = 4.9 Hz,
sept, 3JPOCH = 10.7 Hz, 3JH,H = 6.2 Hz, 2H, OCH), 7.18 (dd,
4JH6,H4 = 1.0 Hz, 1H, C6H, Py), 8.33 (d, JH4,H3 = 8.5 Hz, 1H, C3H, Py),
3
4
3JH5,H4 = 8.3 Hz, JH6,H5 = 4.7 Hz, 1H, C5H, Py), 7.26–7.44 (m, 30H,
4
8.35 (d, JPNCNH = 8.3 Hz, 1H, NH) ppm. 1H NMR (acetone-d6):
PPh3), 7.57 (d, 4JPNCNH = 7.6 Hz, 1H, NH), 8.02 (ddd, 3JH5,H4 = 8.3 Hz,
4JH4,H2 = 2.5 Hz, 4JH6,H4 = 1.4 Hz, 1H, C4H, Py), 8.26 (dd,
3JH6,H5 = 4.7 Hz, 4JH6,H4 = 1.4 Hz, 1H, C6H, Py), 8.60 (d,
4JH4,H2 = 2.5 Hz, 1H, C2H, Py) ppm. 31P{1H} NMR (CDCl3): d = ꢀ1.1
d = 1.25 (br s, 12H, CH3), 4.70 (br s, 2H, OCH), 6.78–7.88, 8.02–
8.87 (m, PPh3 + Py + NH) ppm. 31P{1H} NMR (CDCl3): d = ꢀ1.1 (2P,
PPh3), 55.8 (1P, NPS) ppm. 31P{1H} NMR (acetone-d6): d = ꢀ0.8
(2P, PPh3), 57.4 (1P, NPS) ppm. IR:
m = 604 (P@S), 1020, 1040
(2P, PPh3), 56.1 (1P, NPS) ppm. IR:
m = 570 (P@S), 990, 1020
(POC), 1512 (SCN), 3290 (NH) cmꢀ1. ES-MS (positive ion): m/z
(%) = 855 (26) [Cu3L2]+, 815 (11) [Cu2L2+Na]+, 793 (40) [Cu2L2+H]+,
722 (34) [Cu(PPh3)L+Cu]+, 660 (100) [Cu(PPh3)L+H]+, 589 (36)
[Cu(PPh3)2]+, 396 (82) [CuL+H]+. Anal. Calc. for C49H51Cl2Cu-
(POC), 1510 (SCN), 3224 (NH) cmꢀ1. ES-MS (positive ion): m/z
(%) = 855 (20) [Cu3L2]+, 831 (10) [Cu2L2+K]+, 722 (15) [Cu(PPh3)L+-
Cu]+, 660 (33) [Cu(PPh3)L+H]+, 633 (100) [K(PPh3)L+H]+, 589 (94)
[Cu(PPh3)2]+, 396 (14) [CuL+H]+. Anal. Calc. for C48H49CuN3O2P3S2
(920.52): C, 62.63; H, 5.37; N, 4.56. Found: C, 62.49; H, 5.33; N,
4.60%.
Table 1
2.1.3 Cu(PPh3)Lc (3)
Selected bond lengths (Å), and bond angles (°) for 2
Yield: 1.512 g (75%). M.p. 140 °C. 1H NMR (CDCl3): d = 1.30–1.33
Bond lengths
3
(m, 12H, CH3), 4.23 (s, 2H, NH2), 4.77 (d, sept, JPOCH = 10.7 Hz,
Cu(1)–S(1)
Cu(1)–S(2)
Cu(1)–P(2)
Cu(1)–P(3)
S(1)–P(1)
S(2)–C(1)
P(1)–O(1)
P(1)–O(2)
P(1)–N(1)
N(1)–C(1)
N(2)–C(1)
2.3985(17)
2.3486(15)
2.3387(15)
2.2988(17)
1.991(2)
1.743(6)
1.581(4)
1.599(5)
1.615(5)
Cu(1A)–S(1A)
Cu(1A)–S(2A)
Cu(1A)–P(2A)
Cu(1A)–P(3A)
S(1A)–P(1A)
S(2A)–C(1A)
P(1A)–O(1A)
P(1A)–O(2A)
P(1A)–N(1A)
N(1A)–C(1A)
N(2A)–C(1A)
2.3936(19)
2.3458(17)
2.2939(18)
2.3298(16)
1.981(2)
1.753(7)
1.595(5)
1.599(5)
1.602(5)
3JH,H = 6.2 Hz, 2H, OCH), 6.15 (d, JH5,H4 = 7.8 Hz, 1H, C5H, Py),
3
7.33–7.45 (m, 16H, PPh3+C4H), 7.68 (d, JH3,H4 = 7.9 Hz, 1H, C3H,
3
4
Py), 8.10 (d, JPNCNH = 8.2 Hz, 1H, NH) ppm. 1H NMR (acetone-d6):
3
3
d = 1.29 (d, JH,H = 6.2 Hz, 6H, CH3), 1.30 (d, JH,H = 6.2 Hz, 6H,
3
3
CH3), 4.77 (d, sept, JPOCH = 10.8 Hz, JH,H = 6.2 Hz, 2H, OCH), 5.33
(s, 2H, NH2), 6.24 (d, JH5,H4 = 7.9 Hz, 1H, C5H, Py), 7.37 (t,
3
3JH4,H3 = 3JH4,H5 = 7.9 Hz, 1H, C4H), 7.50–7.56 (m, 16H, PPh3+C3H),
4
8.16 (d, JPNCNH = 8.2 Hz, 1H, NH) ppm. 31P{1H} NMR (CDCl3):
1.323(7)
1.380(7)
1.317(8)
1.358(8)
d = 3.2 (1P, PPh3), 55.0 (1P, NPS) ppm. 31P{1H} NMR (acetone-d6):
Bond angles
d = 3.8 (1P, PPh3), 56.3 (1P, NPS) ppm. IR:
m = 610 (P@S), 990,
S(1)–Cu(1)–S(2)
S(1)–Cu(1)–P(2)
S(1)–Cu(1)–P(3)
S(2)–Cu(1)–P(2)
S(2)–Cu(1)–P(3)
P(2)–Cu(1)–P(3)
Cu(1)–S(1)–P(1)
Cu(1)–S(2)–C(1)
S(1)–P(1)–O(1)
S(1)–P(1)–O(2)
S(1)–P(1)–N(1)
O(1)–P(1)–O(2)
O(1)–P(1)–N(1)
O(2)–P(1)–N(1)
P(1)–N(1)–C(1)
S(2)–C(1)–N(1)
S(2)–C(1)–N(2)
N(1)–C(1)–N(2)
104.28(5)
101.92(6)
113.12(6)
118.19(6)
107.78(6)
111.37(6)
101.53(8)
99.83(18)
113.35(16)
110.95(16)
117.80(17)
101.1(2)
108.6(2)
103.3(2)
127.8(4)
127.8(4)
115.0(4)
117.2(5)
S(1A)–Cu(1A)–S(2A)
S(1A)–Cu(1A)–P(2A)
S(1A)–Cu(1A)–P(3A)
S(2A)–Cu(1A)–P(2A)
S(2A)–Cu(1A)–P(3A)
P(2A)–Cu(1A)–P(3A)
Cu(1A)–S(1A)–P(1A)
Cu(1A)–S(2A)–C(1A)
S(1A)–P(1A)–O(1A)
S(1A)–P(1A)–O(2A)
S(1A)–P(1A)–N(1A)
O(1A)–P(1A)–O(2A)
O(1A)–P(1A)–N(1A)
O(2A)–P(1A)–N(1A)
P(1A)–N(1A)–C(1A)
S(2A)–C(1A)–N(1A)
S(2A)–C(1A)–N(2A)
N(1A)–C(1A)–N(2A)
103.81(6)
109.36(6)
104.91(7)
109.39(6)
115.41(6)
113.29(6)
101.52(9)
101.9(2)
109.9(2)
116.8(3)
119.39(19)
101.1(3)
104.5(3)
103.0(3)
128.9(5)
127.7(5)
115.0(5)
117.3(6)
1005, 1010 (POC), 1520 (SCN), 1610 (NH2) 3200–3400 (NH+NH2)
cmꢀ1. ES-MS (positive ion): m/z (%) = 1297 (49) [Cu4L3]+, 885 (24)
[Cu3L2]+, 823 (29) [Cu2L2+H]+, 675 (100) [Cu(PPh3)L+H]+, 589 (8)
[Cu(PPh3)2]+, 411 (54) [CuL+H]+. Anal. Calc. for C30H35CuN4O2P2S2
(673.25): C, 53.52; H, 5.24; N, 8.32. Found: C, 53.39; H, 5.27; N,
8.27%.
2.2. Synthesis of Cun(La–c
) (4–6)
n
A suspension of HLa–c (1 g, 3 mmol) in aqueous ethanol (25 mL)
was mixed with an ethanol solution of KOH (0.185 g, 3.3 mmol).
The resulting mixture was added dropwise to a suspension of CuI
(0.570 g, 3 mmol) in aqueous ethanol (20 mL). The mixture was
stirred at room temperature for 1.5 h. The resulting precipitate of
KI was filtered and the solvent was then removed in vacuum. The