Iridium, Rhodium, and Ruthenium Catalysts for the 鈥淎ldehyde鈥揥ater Shift鈥?Reaction

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• 作者：Timothy P. Brewster ; William C. Ou ; Jeremy C. Tran ; Karen I. Goldberg ; Susan K. Hanson ; Thomas R. Cundari ; D. Michael Heinekey
• 刊名：ACS Catalysis
• 出版年：2014
• 出版时间：September 5, 2014
• 年：2014
• 卷：4
• 期：9
• 页码：3034-3038
• 全文大小：255K
• ISSN：2155-5435

文摘

A series of half-sandwich complexes of iridium, rhodium, and ruthenium are shown to be active catalysts for the conversion of aldehydes and water to carboxylic acids. Depending on the catalyst, H₂ is either released (the 鈥渁ldehyde鈥搘ater shift鈥? or transferred to a second equivalent of aldehyde (aldehyde disproportionation). Mechanistic studies suggest hydride transfer to be the selectivity-determining step along the reaction pathway. Using [(p-cymene)Ru(bpy)OH₂][OTf]₂ as precatalyst, we demonstrate a novel example of a highly selective aldehyde鈥搘ater shift in the absence of a hydrogen acceptor or base.

Keywords:

aldehyde oxidation; homogeneous catalysis; dehydrogenation; disproportionation; water