Haloalkyl complexes of the transition metals. Part 3. Reactions of some chloromethyl and methoxymethyl complexes of molybdenum, tungsten, manganese, rhenium, iron, and ruthenium with some tertiary phosphine and related ligands

Abstract

The reactions of some chloromethyl transition-metal complexes [M′–CH2Cl] with PPh3 have been investigated. For M′= Fe(η5-C5H5)(CO)2 or W(η5-C5H5)(CO)3, cationic ylide complexes of the type [M′–CH2PPh3]+ have been isolated, whereas for M′= Mn(CO)5 or Mo(η5-C5H5)(CO)3, chloro-complexes were obtained and for M′= Re(CO)5 or Ru(η5-C5H5)(CO)2, no ligand products were found under the reaction conditions used. The reactions have been investigated in methanol and acetonitrile. The reactions of [Fe(η5-C5H5)(CO)2(CH2Cl)] with other ligands (L) have also been studied; cationic ylide complexes [Fe(η5-C5H5)(CO)2(CH2L)]+ have been obtained for L = PMe2Ph, PMePh2, PEt2Ph, PEtPh2, or AsPh3 and disubstituted cationic complexes [Fe(η5-C5H5)(CO)L2]+ where L = PMe3, PMe2Ph, PEt2Ph, or PEtPh2. Possible mechanisms for these reactions are discussed. The reactions of some methoxymethyl complexes [M′–CH2OMe] with PPh3 are also described.