Cyclopentadienyl-ruthenium and -osmium chemistry. Part 6. Reactions of alkylruthenium complexes with disubstituted acetylenes

Abstract

Hexafluorobut-2-yne reacts with [RuMe(PPh₃)₂(η-C₅H₅)] in benzene to give the butadienyl complex [[graphic omitted]CMe(CF₃)}(PPh₃)(η-C₅H₅)]. Using 1,2-dimethoxyethane as solvent, the vinyl complex [Ru{C(CF₃):CMe(CF₃)}(CO)(PPh₃)(η-C₅H₅)] has been isolated. With C₂(CF₃)₂, the carbonyl complex [RuMe(CO)(PPh₃)(η-C₅H₅)] affords a diruthenium complex formulated as [(η-C₅H₅)(OC)(Ph₃P)Ru{C(CF₃): C(CF₃)}[graphic omitted]Ph₂)], and the benzyl complex [Ru(CH₂Ph)(PPh₃)₂(η-C₅H₅)] gives a product assigned a structure [[graphic omitted]C(CF₃)H}(PPh₃)(η-C₅H₅)]. Dimethyl acetylenedicarboxylate reacts with [RuMe(PPh₃)₂(η-C₅H₅)] to give [[graphic omitted]CMe(CO₂Me)}(PPh₃)(η-C₅H₅)], [Ru{η⁵-C₅(CO₂Me)₄H₃}(η-C₅H₅)], and [[graphic omitted]OMe}(PPh₃)(η-C₅H₅)]; an analogous product to the latter is obtained from C₂(CO₂Me)₂ and [Ru(CH₂Ph)(PPh₃)₂(η-C₅H₅)]. The hydrido-complex [RuH(CO)(PPh₃)(η-C₅H₅)] reacts with the acetylenic diester to give [Ru{C(CO₂Me):C(CO₂Me)H}(PPh₃)₂(η-C₅H₅)], which reacts further with C₂(CF₃)₂ to give a ruthenocene derivative [Ru{η⁵-C₅(CO₂Me)₂(CF₃)₂(OMe)}(η-C₅H₅)]. 4-Phenylbut-3-yn-2-one and [RuMe(PPh₃)₂(η-C₅H₅)] afford [[graphic omitted]Me}(PPh₃)(η-C₅H₅)] and [[graphic omitted]Me}(PPh₃)(η-C₅H₅)].