Cyclopentadienyl-ruthenium and -osmium chemistry. X. Reactions of vinylidene complexes with alcohols and water: syntheses of alkoxy(alkyl)carbene, acyl and alkyl complexes

Abstract

Simple ligand-exchange reactions between Ru(C2Ph)(PPh3)2(η-C5H5) and L afford Ru(C2Ph)(L)-(PPh3)(η-C5H5) [L = CO, CNBut, PMe3 or P(OMe)3]. These complexes, and other σ-acetylides, Ru(C2R)(PPh3)2(η-C5H5) (R = Me or CO2Me), react with HPF6,OEt2 to give the corresponding vinylidene complexes {Ru(C=CHPh)(L)(PPh3)(η-C5H5)]PF6 or [Ru(C=CHR)(PPh3)2(η- C5H5)}PF6; which in turn react more or less readily with MeOH to give {Ru[C(OMe)CH2Ph](L)(PPh3)(η-C5H5)]PF6 or {Ru[C(OMe)CH2R](PPh3)2(η-C5H5)}PF6; the complexes {Ru[C(OR)CH2Ph](CO)(PPh3)-(η-C5H5)}PF6 (R = Et or Pri) and {Ru[C(OMe)CH2Ph](dppe)(η-C5H5)}PF6 were formed in analogous reactions. Water reacts with [Ru(C=CHPh)(L)(PPh3)(η-C5H5)]PF6 to give RuX(CO)(PPh3)(η-C5H5) (L = PPh3, X = CH2Ph; L = CO, X = COCH2Ph), the former being formed by a spontaneous alkyl migration reaction.