Reaction of fluoro-olefins with iron and ruthenium carbonyl complexes

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.