Metallophosphoranes: The hidden face of transition metal–phosphine complexes

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• 作者：Jenni Goodman ; Stuart A. Macgregor
• 关键词：Metallophosphoranes ; Mechanism ; Density functional theory ; Isomerization ; M– ; X/P– ; R exchange ; Bond activation ; C– ; F activation ; Phosphine ligands
• 刊名：Coordination Chemistry Reviews
• 出版年：2010
• 出版时间：June 2010
• 年：2010
• 卷：254
• 期：11-12
• 页码：1295-1306
• 全文大小：1697 K

文摘

Reactions in which metallophosphoranes, of general formula L_nMPR₄, have been implicated as intermediates or possible transition states are reviewed. Such species can be accessed via nucleophilic attack on metal–phosphine complexes, with the source of nucleophile being either external or internal in the form of an anionic co-ligand. The reverse process, transfer of a group from a {PR₄} ligand to a metal, has also been observed with the formation of a metal phosphine. Thus metallophosphoranes have been postulated to play a role in isomerization processes and novel M–X/P–R exchange reactions. Metallophosphoranes have also been implicated in unusual ‘phosphine-assisted C–F bond activation’ reactions. Recent computational studies on these processes are discussed.