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

Syntheses of Dicarbonyldiphosphineplatinum (O) Complexes and Their Oxidative Addition Reaction with Alkyl Halide

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。在一氧化碳气氛存在下用NaBH_4还原[Pt(diphos)Cl_2]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^(31)P NMR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)X_2]之一[Pt(d(i-Pr)pe)I_2]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。

Reduction of Pt(diphos)Cl_2 with NaBH_4 in THF solution under an atmosphere of carbon monoxide gives dicarbonyldiphosphineplatinum(0)Pt(diphos)(CO)_2 (diphos= depe, dppb, dppp, dppe, d(i-Pr)pe, dppm). Thus it provides a simple and convenient method for the preparation of the title complexes. The complexes.The complexes Pt(diphos)(CO)_2 are readily converted into clustered carbonyl platinum (0) Pt_4 (diphos)_3 (CO)_3, after working up. The reaction of the complexes Pt(diphos)(CO)_2 with R--X (R=Me, Et, C_6H_5, C_6H_5CH_2; X=Cl, Br, I) have been investigated by IR, ~1H NMR and ^(31)P NMR spectra, the molecular structure of oxidative addition product have been determined by X-ray diffration method. The oxidation addition reaction of alkyl halides to platinum (0) complexes is proposed to follow a non-chain radical mechanism.