期刊
TRANSITION METAL CHEMISTRY
卷 29, 期 2, 页码 205-211出版社
SPRINGER
DOI: 10.1023/B:TMCH.0000019423.68981.fa
关键词
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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][H-2]. 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 alpha,beta-unsaturated ketone has been consumed.
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