Stepwise Syntheses of a Series of Thiolate-Bridged Diruthenium Complexes [Cp*RuBr(μ-SPri)2RuCp*X] (Cp* = η5-C5Me5; X = SPri, alkynyl, H) and [Cp*RuR(μ-SPri)2RuCp*H] (R = CH2Ph, CH2CH2Ph). Facile Dinuclear Reductive Elimination of PhCH3 from [Cp*Ru(CH2Ph)(μ-SPri)2RuCp*H]

Abstract

Abstract Diruthenium complex [Cp*Ru(μ-SPri)3RuCp*] (Cp* = η5-C5Me5) reacted with PhCH2Br to give [Cp*RuBr(μ-SPri)2RuCp*(SPri)] (3) and PhCH2CH2Ph. Treatment of 3 with HC≡CR (R = But, 4-MeC6H4) or H2 resulted in the formation of [Cp*RuBr(μ-SPri)2RuCp*(C≡CR)] (4) or [Cp*RuBr(μ-SPri)2RuCp*H] (5), respectively. Complex 5 was further converted into [Cp*RuR(μ-SPri)2RuCp*H] (6a: R = PhCH2; 6b: R = PhCH2CH2) by the reaction with RMgX (X = Cl, Br). In contrast to the inertness of 6b, 6a dissolved in benzene underwent dinuclear reductive elimination to give PhMe in high yield at room temperature, accompanied by the generation of [Cp*Ru(μ-SPri)2RuCp*].