Kinetics and mechanisms of homogeneous catalytic reactions. Part 2. Hydrogenation of cyclohexane catalysed by [RuH(CO)-(NCMe)2(PPh3)2]BF4

Summary Kinetic and mechanistic studies of the homogeneous hydrogenation of cyclohexane were carried out using the cationic complex [RuH(CO)(NCMe)₂(PPh₃)₂]BF₄ as the catalyst precursor, which was very efficient under mild reaction conditions in xylene solution. The experimental rate law was found to ber = {K₁K₂k₃/([MeCN]+K_1–(1+K₂)[C₆H₁₀]}[Ru][C₆H₁₀][H₂], which became {K₂k₃/(1 +K₂)}[Ru][H₂] at high cyclohexane concentrations. The activation parameters were calculated. The kinetic data are consistent with a mechanism involving the oxidative addition of hydrogen as the rate-determining step of the catalytic cycle.