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)].