Reaction of fluoro-olefins with iron and ruthenium carbonyl complexes

Abstract

The photochemical reaction of fluoro-olefins with the zero-valent iron and ruthenium complexes trans-[M(CO)₃L₂](L = phosphite or phosphine; M = Fe or Ru), led to the oxidative-elimination of carbon monoxide and the formation of the stable crystalline compounds [M(CO)₂L₂(fluoro-olefin)](L = phosphite or phosphine; M = Fe or Ru; fluoro-olefin = C₂F₄, C₂F₃H, C₂F₃CF₃, C₂F₃Cl, or cyclo-C₄F₆). Phosphite ligands adopt a relative cis-configuration, whereas, phosphines retain their relative trans-configuration on reaction with fluoro-olefins. In contrast, trifluoroethylene reacts with trans-[Fe(CO)₃{EtO)₃P}₂] to afford a hexafluoroferracyclopentane complex. Chlorotrifluoroethylene reacts with trans-[Ru(CO)₃(PhPMe₂)₂] to form an isomeric mixture of trifluorovinyl–ruthenium complexes. The mechanism of formation and the bonding of these complexes is discussed.