Article
Organometallics, Vol. 30, No. 3, 2011 601
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the reaction was monitored by H NMR. During this time, the
840.594 ([M þ NH4, requires 840.331). Crystals of 7 suitable for
X-ray study were grown from a CH2Cl2 solution by a slow
evaporation of the solvent at room temperature.
initially pale yellow solution turned colorless, and the colorless
precipitate of NaCl and the known Na2[Pt(CN)4]78,79 (ESI--MS
149.4894, calcd 149.4885) was formed. Free heterocycles were
separated from excess NaCN (and also from NaCl and Na2[Pt-
(CN)4] formed in the reaction) by evaporation of the solvent at
room temperature and treating the colorless, oily residue with
CH2Cl2. The liquid phase was separated by filtration, and evapora-
tion of the solvent afforded heterocycles 10-13 as colorless, oily
residues in almost quantitative yields.
10. 1H NMR δH (300 MHz, CDCl3): 0.82 (3H, s, CH3), 0.90
(2H, m, CH2), 1.000 (6H, s, two CH3), 1.22 (3H, t, J = 7.5 Hz,
CH3), 1.44 (1H, m, CH2), 1.57 (3H, s, CH3), 1.73 (1H, m, CH2),
2.13 (1H, d, J4 Hz, CH), 2.34 (1H, q, J=7.5 Hz, CH2), 3.02 (1H, d,
J = 7 Hz, CH), 3.82 (1H, d, J = 7 Hz, CH). 13C NMR δC (75.5
MHz, CDCl3): 10.1 (CH3), 10.8 (CH3), 19.4 (CH3), 20.3 (CH2),
22.1 (CH3), 23.8 (CH3), 25.6 (CH2), 31.7 (CH2), 46.2 (C9), 47.7
(C5), 48.5 (CH), 78.3 (CH), 87.1 (CH), 121.5 (C3a), 167.9 (C2). MS:
m/z (high-resolution ESIþ) 265.192 (M þ H, requires 265.192).
8. Yield: 32.6 mg (71%). Anal. Found: C, 49.54; H, 5.49; N,
5.35. Calcd for C40H52N4Cl2PtO4 1/2CHCl3: C, 49.71; H, 5.41; N,
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5.73. Rf = 0.70 (CHCl3/Me2CO, 16:1, v/v). IR νmax (KBr)/cm-1
:
2957 m-s (CH), 1632 s (CdN). 1H NMR δH (300 MHz, CDCl3):
0.84 (3H, s, CH3), 0.95 (3H, t, J = 7 Hz, CH3), 1.03 (3H, s, CH3),
1.08 (3H, s, CH3), 0.8-1.00 (2H, m, CH2), 1.30-1.40 (1H, m,
CH2), 1.63-1.80 (1H, m, CH2), 1.96 (1H, m, J = 7 Hz, CH2 from
Et), 2.23 (1H, d, J = 4 Hz, CH), 3.08 (1H, q, J = 7 Hz, CH2 from
Et), 3.18 (1H, d, J = 8 Hz, CH), 4.66 (1H, d, J = 8 Hz, CH), 7.64
(3H, m, Ph), 9.39 (2H, d, J = 7 Hz, Ph). 13C NMR δC (75.5 MHz,
CDCl3): 8.0 (CH3), 10.8 (CH3), 19.4 (CH3), 22.1 (CH3), 25.2
(CH2), 29.4 (CH2), 31.5 (CH2), 46.3 (CH), 47.7 (C9),48.1 (C5),
77.8 (CH), 87.9 (CH), 122.8 (C3a), 123.3 (Cipso), 128.5, 131.1, and
133.8 (Ph), 165.6 (C2). MS: m/z (high-resolution ESIþ) 919.429 (M
þ H, requires 919.304). Crystals of 8 CHCl3 suitable for an X-ray
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11. 1H NMR δH (300 MHz, CDCl3): 0.86 (3H, s, CH3),
0.87-1.00 (2H, m, CH2), 1.03 (3H, s, CH3), 1.07 (3H, s, CH3),
1.20 (1H, m, CH2), 1.70 (3H, s, CH3), 1.71-1.78 (1H, m, CH2),
2.22 (1H, d, J = 4 Hz, CH), 3.19 (1H, d, J = 8 Hz, CH), 3.90
(1H, d, J = 8 Hz, CH), 7.47 (2H, m, m-Ph), 7.55 (1H, m, p-Ph),
7.98 (2H, d, J = 7 Hz, o-Ph). 13C NMR δC (75.5 MHz, CDCl3):
10.7 (CH3), 19.5 (CH3), 22.2 (CH3), 23.8 (CH3), 25.6 (CH2), 31.7
(CH2), 46.3 (C9), 47.8 (C5), 48.5 (CH), 78.2 (CH), 87.3 (CH),
121.9 (C3a), 125.5 (Cipso), 128.6, and 132.3 (Ph), 162.7 (C2). MS:
m/z (high-resolution ESIþ) 313.192 (M þ H, requires 313.192).
study were grown from a CHCl3 solution by a slow evaporation of
the solvent at room temperature.
9. Yield: 33.3 mg (78%). Anal. Found: C, 44.80; H, 6.30; N,
9.61. Calcd for C32H54N6Cl2PtO4: C, 45.07; H, 6.38; N, 9.85. Rf =
0.50 (CHCl3/Me2CO, 16:1, v/v). IR νmax (KBr)/cm-1: 2955 m-s
(CH), 1669 s (CdN). 1H NMR δH (300 MHz, CDCl3): 0.84 (3H, s,
CH3), 0.88 (3H, t, J = 7.2 Hz, CH3), 0.99 (3H, s, CH3), 1.01 (3H, s,
CH3), 1.15-1.27 (1H, m), 1.42 (1H, m, CH2), 1.72-1.78 (2H, m,
J = 7.1 Hz, CH2), 2.13 (1H, d, J = 4 Hz, CH), 2.78 (2H, m, CH2),
3.08 (1H, d, J= 7 Hz, CH), 3.75 (6H, s, br, NMe2), 4.90 (1H, d, J=
8 Hz, CH). 13C NMR δC (75.5 MHz, CDCl3): 8.1 (CH3), 10.7
(CH3), 19.4 (CH3), 22.1 (CH3), 25.4 (CH2), 30.4 (CH2), 31.8 (CH2),
39.8 (br, NMe2), 46.5 (CH), 47.4 (C9), 48.0(C5), 77.6 (CH), 87.1
(CH), 120.5 (C3a), 159.4 (C2). MS: m/z (high-resolution ESIþ)
12. 1H NMR δH (300 MHz, CDCl3): 0.82 (3H, s, CH3),
0.90-0.98 (5H, m þ t, CH2 and CH3), 0.94 (3H, s, CH3), 0.98
(6H, s, CH3), 1.24 (3H, t, J = 7.5 Hz, CH3), 1.43 (1H, m), 1.78 (2H,
m, two CH2), 1.98 (1H, m, CH2), 2.14 (1H, d, J= 4.5 Hz, CH), 2.35
(2H, q,J=7.5Hz,CH2), 3.03 (1H, d, J= 7.3 Hz, CH), 3.81 (1H, d,
J= 7.5 Hz, CH). 13CNMRδC (75.5 MHz, CDCl3):7.7(CH3), 10.3
(CH3), 10.8 (CH3), 19.4 (CH3), 20.4 (CH2), 22.1 (CH3), 25.7 (CH2),
30.7 (CH2), 31.7 (CH2), 46.0 (C9), 47.8 (C5), 48.4 (CH), 78.8 (CH),
86.7 (CH), 123.7 (C3a), 167.9 (C2). MS: m/z (high-resolution ESIþ)
279.211 (M þ H, requires 279.207).
853.413 (M þ H, requires 853.326). Crystals of 9 Me2CO suitable
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for an X-ray study were grown from an acetone solution by a slow
evaporation of the solvent at room temperature.
Liberation of Dihydro-1,2,4-oxadiazoles from 4, 5, 7, and 8. An
excess of NaCN (11.8 mg, 0.24 mmol) in methanol-d4 (0.5 mL) was
added to a solution of the corresponding [PtCl2(dihydro-1,2,4-oxa-
diazole)2] complex 4, 5, 7, and 8 (0.03 mmol) in CD2Cl2 (0.5 mL),
and the reaction mixture was left to stand at 35 °C; completeness of
13. 1H NMR δH (300 MHz, CDCl3): 0.85 (3H, s, CH3), 0.89
(3H, t, J = 7 Hz, CH3), 1.02 (3H, s, CH3), 1.05 (3H, s, CH3),
(78) Kharitonov, Y. Y.; Evstaf’eva, O. N.; Baranovskii, I. B.; Mazo,
G. Y. Zh. Neorg. Khim. 1968, 13, 827.
(79) Kharitonov, Y. Y.; Evstaf’eva, O. N.; Baranovskii, I. B.; Mazo,
G. Y.; Babaeva, A. V. Zh. Neorg. Khim. 1966, 11, 1733.