Vicente et al.
Compound 4a. Yield: 98%. Anal. Calcd for C20H35N3O2PdS2:
C, 46.19; H, 6.78; N, 8.08; S, 12.33. Found: C, 46.11; H, 7.08; N,
8.19; S, 11.83. Mp: 135 °C (dec). ΛM (Ω-1 cm2 mol-1): 0. IR
(cm-1): ν(NH) 3359; ν(CN) 2190; ν(CO, CdC) 1663, 1606, 1526.
) 7 Hz), 1.42 (“t”, ABX3, 3 H, CH2Me, JHH ) 7 Hz), 2.06 [s, 3 H,
C(O)Me], 2.20 [s, 6 H, Me (Xy)], 2.26 [s, 3 H, Me (Xy)], 2.28 [s,
3 H, Me (Xy)], 2.40 [s, 3 H, C(O)Me], 3.59 (m, ABX3, 2 H, CH2),
4.19 (m, ABX3, 1 H, CH2), 4.78 (m, ABX3, 1 H, CH2), 6.85 [“t”,
0.5 H, NH, JNH ) 9 Hz), 7.06-7.23 (m, 6 H, C6H3), 7.46 (s, 0.5
H, NH). 1H NMR (+55 °C): 1.34-1.47 (m, ABX3, 6 H, CH2Me),
2.22 [s, 6 H, Me (Xy)], 2.27 [s, br, 6 H, C(O)Me], 2.29 [s, 6 H,
Me (Xy)], 3.52 (m, br, ABX3, 2 H, CH2), 4.29 (m, br, ABX3, 1 H,
CH2), 4.73 (m, br, ABX3, 1 H CH2], 6.92-7.40 (m, 7 H, NH +
1H NMR (200 MHz, 25 °C): δ 1.15 (“t”, ABX3, 3 H, CH2Me, J
HH
) 7 Hz), 1.31 (“t”, ABX3, 3 H, CH2Me, JHH ) 7 Hz), 1.47 (s, 9 H,
tBu), 1.70 (s, 9 H, tBu), 2.35 [s, 3 H, C(O)Me], 2.45 [s, 3 H, C(O)-
Me], 3.02 (m, ABX3, 1 H, CH2), 3.28 (m, ABX3, 1 H, CH2), 4.09
(m, ABX3, 1 H, CH2), 4.82 (m, ABX3, 1 H, CH2), 5.67 (s, 1 H,
1
1
NH). H NMR (+50 °C): 1.22 (m, ABX3, 6 H, CH2Me), 1.42 (s,
C6H3). H NMR (-50 °C): 1.21-1.44 (m, ABX3, 6 H, CH2Me),
9 H, tBu), 1.70 (s, 9 H, tBu), 2.38 [s, 6 H, C(O)Me], 3.00 (m, ABX3,
1 H, CH2), 3.27 (m, ABX3, 1 H, CH2), 4.13 (m, ABX3, 1 H, CH2),
4.74 (m, ABX3, 1 H, CH2) 5.66 (s, 1 H, NH). 1H NMR (-50 °C):
1.15 (“t”, ABX3, 3 H, CH2Me, JHH ) 7 Hz), 1.30 (“t”, ABX3, 3 H,
2.02 [s, 3 H, C(O)Me], 2.21 [s, 9 H, Me (Xy)], 2.27 [s, 3 H, Me
(Xy)], 2.41 [s, 3 H, C(O)Me], 3.55 (m, ABX3, 2 H, CH2), 4.10 (m,
ABX3, 1 H, CH2), 4.79 (m, ABX3, 1 H, CH2), 6.84 [“t”, 0.5 H, NH,
JNH ) 9 Hz], 7.10-7.40 (m, 6 H, C6H3), 7.92 (s, 0.5 H, NH).
[M{η2-(S,S′)-S2CdC{C(O)Me}2}(CNtBu){C(NH2)(NHtBu)}]
[M ) Pd (6a), Pt (6b)]. NH3 was bubbled through a solution of
1a (250 mg, 0.56 mmol) or 1b (286.0 mg, 0.53 mmol) in THF (60
mL) for 1 h. The resulting solution was stirred for 15 h and
concentrated under vacuum (3 mL), and Et2O (60 mL) was added
to precipitate a cream solid that was filtered, washed with Et2O (2
× 10 mL), and suction dried. Compound 6a is hygroscopic and
must be filtered and dried under nitrogen.
t
t
CH2Me, JHH ) 7 Hz), 1.50 (s, 9 H, Bu), 1.71 (s, 9 H, Bu), 2.35
[s, 3 H, C(O)Me], 2.53 [s, 3 H, C(O)Me], 3.10 (m, ABX3, 1 H,
CH2), 3.30 (m, ABX3, 1 H, CH2), 3.97 (m, ABX3, 1 H, CH2), 4.96
(m, ABX3, 1 H, CH2), 5.70 (s, 1 H, NH). Crystals of 4a suitable
for an X-ray diffraction study grew from CH2Cl2 and Et2O by the
liquid diffusion method.
Compound 4b. Yield: 96%. Anal. Calcd for C20H35N3O2PtS2:
C, 39.58; H, 6.26; N, 7.13; S, 9.75. Found: C, 39.46; H, 5.80; N,
6.90; S, 10.23. Mp: 142 °C (dec). ΛM (Ω-1 cm2 mol-1): 0. IR
(cm-1): ν(NH) 3376, ν(CN) 2182; ν(CO, CdC) 1666, 1608, 1530.
1H NMR (200 MHz, 25 °C): δ 1.17 (“t”, ABX3, 3 H, CH2Me, JHH
) 7 Hz), 1.29 (“t”, ABX3, 3 H, CH2Me, JHH ) 7 Hz), 1.46 (s, 9 H,
Compound 6a. Yield: 235 mg, 91%. Anal. Calcd for C16H27N3O2-
PdS2: C, 41.42; H, 5.87; N, 9.06; S, 13.82. Found: C, 41.13; H,
5.91; N, 9.34; S, 13.56. Mp: 149 °C (dec). ΛM (Ω-1 cm2 mol-1):
0. IR (cm-1): ν(NH) 3430, 3205; ν(CN) 2200; ν(CO, CdC) 1684,
t
tBu), 1.72 (s, 9 H, Bu), 2.32 [s, 3 H,C(O)Me], 2.47 [s, 3 H,C(O)-
1
t
1616. H NMR (d6-DMSO): δ 1.44 (s, 9 H, Bu), 1.45 (s, 9 H,
tBu), 1.50 (s, 9 H, tBu), 1.52 (s, 9 H, tBu), 2.07 [s, 6 H, C(O)Me],
2.22 [s, 6 H, C(O)Me], 7.10 (s, 1 H, NH), 7.21 (s, 1 H, NH), 8.01
(s, 2 H, NH2), 8.16 (s, 2 H, NH2).
Me], 3.04 (m, ABX3, 1 H, CH2), 3.31 (m, ABX3, 1 H, CH2), 4.13
(m, ABX3, 1 H, CH2), 4.92 (m, ABX3, 1 H, CH2), 5.77 (s, 1 H,
1
NH, JPtH ) 86 Hz). H NMR (+50 °C): 1.28 (“t”, ABX3, 6 H,
CH2Me), 1.45 (s, 9 H, tBu), 1.72 (s, 9 H, tBu), 2.37 [s, 6 H, C(O)-
Me], 3.00 (m, ABX3, 4 H, CH2), 5.77 (s, 1 H, NH, JPtH ) 88 Hz).
1H NMR (-50 °C): 1.17 (“t”, ABX3, 3 H, CH2Me), 1.28 (“t”,
ABX3, 3 H, CH2Me), 1.48 (s, 9 H, tBu), 1.72 (s, 9 H, tBu), 2.34 [s,
3 H,C(O)Me], 2.54 [s, 3 H, C(O)Me], 3.05 (m, ABX3, 1 H, CH2),
3.32 (m, ABX3, 1 H, CH2), 3.95 (m, ABX3, 1 H, CH2), 5.06 (m,
ABX3, 1 H, CH2), 5.79 (s, 1 H, NH, JPtH ) 84 Hz). Crystals of 4b
suitable for an X-ray diffraction study grew from CH2Cl2 and Et2O
by the liquid diffusion method.
Compound 6b. Yield: 275 mg, 94%. Anal. Calcd for C16H27N3O2-
PtS2: C, 34.78; H, 4.92; N, 7.60; S, 11.60. Found: C, 35.19; H,
5.05; N, 7.63; S, 11.50. Mp: 159 °C (dec). ΛM (Ω-1 cm2 mol-1):
0. IR (cm-1): ν(NH) 3401,3315, 3269, 3228; ν(CN) 2183; ν(CO,
1
CdC) 1681, 1627, 1588. H NMR (d6-DMSO): δ 1.26 (s, 9 H,
tBu), 1.42 (s, 9 H, tBu), 1.45 (s, 9 H, tBu), 1.53 (s, 9 H, tBu), 2.14
[s, 3 H, C(O)Me], 2.16 [s, 3 H, C(O)Me], 2.21 [s, 6 H, C(O)Me],
7.27 (s, 1 H, NH), 7.38 (s, 1 H, NH), 7.89 (s, 2 H, NH2), 8.09 (s,
2 H, NH2).
Compound 5a. Yield: 94%. Anal. Calcd for C28H35N3O2PdS2:
C, 54.58; H, 5.73; N, 6.82; S, 10.41. Found: C, 54.77; H, 5.76; N,
6.90; S, 10.02. Mp: 158 °C (dec). ΛM (Ω-1 cm2 mol-1): 0. IR
(cm-1): ν(NH) 3249, ν(CN) 2165, ν(CO, CdC) 1678, 1597, 1530.
1H NMR (200 MHz, 25 °C): δ 1.33 (“t”, ABX3, 3 H, CH2Me, JHH
) 7 Hz), 1.43 (“t”, ABX3, 3 H, CH2Me, JHH ) 7 Hz), 2.11 [s, 3 H,
C(O)Me], 2.25 [s, 6 H, Me (Xy)], 2.29 [s, 6 H, Me (Xy)], 2.42 [s,
3 H, C(O)Me], 2.94 (m, ABX3, 1 H, CH2), 3.57 (m, ABX3, 1 H,
CH2), 4.14 (m, ABX3, 1 H, CH2), 4.69 (m, ABX3, 1 H, CH2), 6.90
[M{η2-(S,S′)-S2CdC{C(O)Me}2}{C(NH2)(NHXy)}2] [M ) Pd
(7a), Pt (7b)]. NH3 was bubbled through a solution of 2a (227.0
mg, 0.51 mmol) or 2b (422.8 mg, 0.67 mmol) in THF (60 mL) for
1 h. A precipitate immediately formed. The suspension was stirred
for 15 h and filtered and the cream solid washed with Et2O (3 ×
10 mL) and suction dried.
Compound 7a. Yield: 245.0 mg, 83%. Anal. Calcd for
C24H30N4O2PdS2: C, 49.96; H, 5.24; N, 9.71; S, 11.11. Found: C,
49.93; H, 5.29; N, 9.74; S, 11.03. Mp: 187 °C (dec). ΛM (Ω-1
cm2 mol-1): 0. IR (cm-1): ν(NH) 3380, 3273, 3182; ν(CO, Cd
1
(m, 1 H, NH), 7.08-7.43 (m, 6 H, C6H3). H NMR (+ 50 °C):
1.29-1.48 (m, ABX3, 6 H, CH2Me), 2.26 [s, 6 H, Me (Xy)], 2.27
[s, br, 6 H, C(O)Me], 2.29 [s, 6 H, Me (Xy)], 2.96 (m, ABX3, 1 H,
CH2), 3.51 (m, ABX3, 1 H, CH2), 4.21 (m, ABX3, 1 H, CH2), 4.65
(m, ABX3, 1 H, CH2), 7.08-7.43 (m, 7 H, C6H3 + NH). 1H NMR
(-50 °C): 1.31-1.42 (m, ABX3, 6 H, CH2Me), 2.06 [s, 3 H, C(O)-
Me], 2.21 [s, 3 H, Me (Xy)], 2.25 [s, 9 H, Me (Xy)], 2.40 [s, 3 H,
C(O)Me], 2.87 (m, ABX3, 1 H, CH2), 3.55 (m, ABX3, 2 H, CH2),
4.05 (m, ABX3, 1 H, CH2), 4.72 (m, ABX3, 1 H, CH2), 6.88 [“t”,
0.5 H, NH], 7.13-7.40 (m, 6 H, C6H3), 7.97 (s, br, 0.5 H, NH).
Compound 5b. Yield: 89%. Anal. Calcd for C28H35N3O2PtS2:
C, 47.72; H, 5.01; N, 5.96; S, 9.10. Found: C, 47.87; H, 5.04; N,
6.17; S, 8.77. Mp: 236 °C (dec). ΛM (Ω-1 cm2 mol-1): 2. IR
(cm-1): ν(NH) 3263, ν(CN) 2155; ν(CO, CdC) 1680, 1601, 1530.
1H NMR (200 MHz, 25 °C): δ 1.34 (“t”, ABX3, 3 H, CH2Me, JHH
1
C) 1690, 1635, 1557. H NMR (d6-DMSO): δ 2.10 [s, 12 H, Me
(Xy)], 2.24 [s, 6 H, C(O)Me], 6.77 (s, 2 H, NH2), 7.13 (m, 6 H,
C6H3), 7.81 (s, 2 H, NH2), 9.48 (s, 2 H, NH). 13C{1H} NMR: δ
17.72 [s, Me (Xy)], 31.80 [s, C(O)Me], 127.69 (s, p-CH, Xy),
128.26 (s, m-CH, Xy), 134.02 (s, ipso-C, Xy), 135.45 (s, o-C, Xy),
139.51 [s, CdS2], 195.33 [s, CdCS2], 196.89 (s, PdCN2), 198.38
(s, CO). 13C-DEPT{1H} NMR: δ 21.26 [s, Me (Xy)], 35.34 [s,
C(O)Me], 131.28 (s, p-CH, Xy), 131.83 (s, m-CH, Xy).
Compound 7b. Yield: 410 mg, 92%. Anal. Calcd for C24H30N4O2-
PtS2: C, 43.30 H, 4.54; N, 8.42; S, 9.63. Found: C, 43.70; H,
4.79; N, 8.36; S, 9.27. Mp: 205 °C (dec). ΛM (Ω-1 cm2 mol-1):
0. IR (cm-1): ν(NH) 3392, 3265, 3179; ν(CO, CdC) 1686, 1606,
1550. 1H NMR (d6-DMSO): δ 2.09 [s, 12 H, Me (Xy)], 2.24 [s, 6
4270 Inorganic Chemistry, Vol. 42, No. 14, 2003