Formation of carbonylrhodium complexes in reactions with fluoroolefins

Abstract

A variety of fluoro-olefins react with RhCl(PPh₃)₃ and Rh₂Cl₂L₄ to give the carbonyl complexes RhCl(CO)L₂[L = Ph₃P, (C₆F₅)₃P, (C₆F₅)₂PhP, or (C₆F₅)Ph₂P]. It is suggested that the carbon monoxide is formed by the action of small traces of water present in the reactions on fluoro-olefin complexes of the type RhCl(fluoro-olefin)L₂. The action of hydrogen chloride on RhCl(C₂F₃X)(PPh₃)₂ gives the fluoroethyl complexes RhCl₂(CFX·CF₂H)(PPh₃)₂, (X = H, F, or Cl) and it is proposed that this type of rearrangement occurs in some of the hydrolysis reactions of the complexes RhCl(fluoro-olefin)L₂. N.m.r. data on the fluoroethyl complexes are given.