Kinetics and mechanisms of homogeneous catalytic reactions. Part 4. Hydrogenation of cyclohexanone and 2-cyclohexen-1-one catalysed by the complexes [MH(CO)(NCMe)2(PPh3)2]BF4 (M = Ru,Os)

Kinetic and mechanistic studies of the homogeneous hydrogenation of cyclohexanone were carried out using the cationic complexes [MH(CO)(NCMe)₂(PPh₃)₂]BF₄ (M = Ru, Os) as the catalyst precursors, which were very efficient under mild reaction conditions in 2-methoxyethanol solution. For both complexes, the catalytic hydrogenation of cyclohexanone proceeds according to the rate law r = k[M][H₂]. The activation parameters were also calculated, the activation energy for the osmium catalyst being higher than for the ruthenium(I). All experimental data are consistent with a mechanism involving the oxidative addition of hydrogen as the rate-determining step of the catalytic cycle. Finally, the [MH(CO)(NCMe)₂(PPh₃)₂]BF₄ complexes were efficient precatalysts for the selective reduction of 2-cyclohexen-1-one to cyclohexanone; the reduction of the CO group of cyclohexanone only begins to take place when the ,-unsaturated ketone has been consumed.