Reactions of co-ordinated ligands. Part III. Mechanism of the rearrangement of platinum chlorofluoro-olefin complexes

Abstract

Activation parameters have been measured for the rearrangement of [[graphic omitted]FXL₂] to [PtX(CFCF₂)L₂](L = PPh₃, X = Cl or Br; L = PMePh₂, X = Cl). The results are compared with those previously obtained for the rearrangement of the related chloro-olefin complexes. The stereochemistry of the rearrangement of cis- and trans-[[graphic omitted]FClL₂](L = PPh₃ or PMePh₂) to [PtCl(cis-CFCFCl)L₂] and [PtCl(trans-CFCFCl)L₂] have been studied, the stereochemistry of the fluoro-olefin being retained. A mechanism involving an intimate ion-pair is discussed.