Cyclopentadienyl-ruthenium and -osmium chemistry. Part 20. Synthesis and X-ray structure of a cationic ruthenium–vinylidene complex, [Ru(CCHMe)(PMe3)2(η-C5H5)]PF6

Abstract

The complexes [Ru(CCR)(PMe₃)L(η-C₅H₅)](R = Me or Ph, L = PMe₃: R = Ph, L = PPh₃) were obtained from reactions between [Ru(CCR)(PPh₃)₂(η-C₅H₅)] and PMe₃, while [Ru(CCHR)(PMe₃)₂(η-C₅H₅)]PF₆(R = H, Me, or Ph) were formed from [RuCl(PMe₃)₂(η-C₅H₅)], HCCR, and NH₄PF₆. Alkylation of [Ru(CCPh)(PMe₃)₂(η-C₅H₅)] with OMe₃PF₆ gave [Ru(CCMePh)(PMe₃)₂(η-C₅H₅)]PF₆. The molecular structure of [Ru(CCHMe)(PMe₃)₂(η-C₅H₅)]PF₆ is described. It has the distorted ‘piano-stool’ configuration, with the plane of the vinylidene ligand bisecting the molecular symmetry plane. For the vinylidene ligand, Ru–C 1.845(7), C–C 1.313(10)Å, Ru–CC 180(2) and C–C–Me 125.1(6)°.