Generation of the 15-Electron Rhodium(II) Complex [RhCl(PPh<sub>3</sub>)<sub>3</sub>]<sup>+</sup> by 1-Electron Oxidation of Wilkinson's Catalyst
作者:Frédéric Barrière、William E. Geiger
DOI:10.1021/om010077b
日期:2001.5.1
Wilkinson's catalyst, RhCl(PPh3)3 (1), undergoes a one-electron oxidation at a sufficiently low potential (E1/2 = +0.035 V vs Fc) to allow a facile electron-transfer reaction with mild oxidants such as the ferrocenium ion. The Rh(II) cation 1+ decomposes rapidly to the very reactive intermediate 2, which over longer reaction times gives rise to the three-coordinate complex [Rh(PPh3)3]+ (4).
威尔金森(Wilkinson)的催化剂RhCl(PPh 3)3(1)在足够低的电势下(E 1/2 = +0.035 V vs Fc)进行单电子氧化,以实现与弱氧化剂(如HCl)的便捷电子转移反应。二茂铁离子。Rh(II)阳离子1 +迅速分解为反应性很强的中间体2,该中间体在更长的反应时间内会生成三配位络合物[Rh(PPh 3)3 ] +(4)。