期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 652, 期 1-2, 页码 105-111出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/S0022-328X(02)01316-5
关键词
hydrogen transfer; transfer hydrogenation; metal catalysis; metal hydrides
Catalytic hydrogen transfer reactions involving transfer hydrogenation of ketones, imines as well as Oppenauer-type oxidation of alcohols occur via active transition metal hydride intermediates. In the RuCl2(PPh3)(3)-catalyzed hydrogen transfer reaction a dramatic rate enhancement by base was observed. It was found that the role of base is to generate a highly active dihydride catalyst RuH2(PPh3)(3). The mechanism of Ru-, Rh-, and Ir-catalyzed hydrogen transfer was probed by using a-deuterated alcohol as hydrogen donor and measuring the amount of deuterium transferred to the keto carbon of the hydrogen acceptor. Two different mechanisms are proposed for the transition metal-catalyzed hydrogen transfer, one via a monohydride (giving a high D-content) and another via a dihydride (giving about half of D-content). (C) 2002 Published by Elsevier Science B.V.
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