Preparation, and mechanism of formation, of alkyl and phenyl complexes of ruthenium(II)

Abstract

New alkyl and phenyl complexes [Ru(CO)₂L₂ClR](L = PMe₂Ph or PMePh₂: R = Me, Et, or Ph) have been prepared by reaction of the all-trans- or all-cis-isomers of [Ru(CO)₂L₂Cl₂] with HgR₂ or SnMe₄: the cis-isomers of [Ru(CO)₂L₂Cl₂] do not react with these reagents. Mechanisms for the reactions, involving initial dissociation of a carbonyl ligand, are proposed on the basis of information about their stereochemistry and kinetics, and studies of halide-exchange reactions of all-trans-[Ru(CO)₂(PMe₂Ph)₂Cl₂] with bromide and iodtde ion. In the case of reactions between [Ru(CO)(PMe₂Ph)₃Cl₂] and HgR₂, in which complexes [Ru(CO)(PMe₂Ph)₃ClR] are formed as intermediates, the transfer of alkyl or phsnyl ligand between mercury and ruthenium has been found to be reversible.