双羰基双膦合铂(O)配合物的合成及其与卤代烃的氧化加成反应

本文报道一种合成标题配合物Pt(diphos)(CO)2的简便方法及其与碳-卤键的氧化加成反应. 在一氧公碳气氛存在下用NaBH4还原Pt(diphos)Cl2]可“原位"得到Pt(diphos)(CO)2]的THF溶液, 能与卤代烃发生氧化加成反应, 并用^1H NMR和^3^1PNMR谱进行了研究. 氧化加成反应按自由基非链式机理进行, 加成产物Pt(diphos)X2]之一Pt(d(i-Pr)pe)I2]经过分子结构测定, 反应能力与卤代烃和双膦螯合配体的电子性质有关.

Syntheses of dicarbonyldiphosphine platinum (O) complexes and their oxidative addition reaction with alkyl halide

The reduction of PtLCl2 (L = R2P(CH2)nPR2) n = 2, R = Et, Ph, CHMe2; n = 1, 3, 4, R = Ph) by NaBH4 in THF under CO atomsphere gave PtL(CO)2. On work-up PtL(CO)2 were converted to Pt4L3(CO)3 clusters. The oxidative substitution reactions of PtL(CO)2 with RX (R = Me, Et, Ph, PhCH2; X = Cl, Br, I) were studied by IR and 1H and 31P NMR spectra; the oxidative substitution products are PtLX2 and in some cases Me complexes as the oxidative addition products. PtLX2 (L = (Me2CH)2PCH2CH2P(CHMe2)2) is orthorhombic, space group I4c2, a 15.14321, b 15.14321, c 19.16199 ? Z = 8, R = 0.0489.