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.