Iridium, Rhodium, and Ruthenium Catalysts for the "Aldehyde-Water Shift" Reaction

被引：46

作者：

Brewster, Timothy P. ^{[1
]}

Ou, William C. ^{[3
]}

Tran, Jeremy C. ^{[1
]}

Goldberg, Karen I. ^{[1
]}

Hanson, Susan K. ^{[2
]}

Cundari, Thomas R. ^{[3
]}

Heinekey, D. Michael ^{[1
]}

机构：

[1] Univ Washington, Dept Chem, Seattle, WA 98195 USA

[2] Los Alamos Natl Lab, Div Chem, Los Alamos, NM 87545 USA

[3] Univ N Texas, Dept Chem, Ctr Adv Sci Comp & Modeling CASCaM, Denton, TX 76203 USA

来源：

ACS CATALYSIS | 2014年 / 4卷 / 09期

基金：

美国国家科学基金会;

关键词：

aldehyde oxidation; homogeneous catalysis; dehydrogenation; disproportionation; water; OXYGEN-ATOM SOURCE; HYDROGEN-PRODUCTION; CARBON-DIOXIDE; ACETIC-ACID; ALCOHOLS; COMPLEXES; METHANOL; H-2; AMINES; LIGAND;

D O I：

10.1021/cs500843a

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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, H-2 is either released (the "aldehyde-water shift") 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-water shift in the absence of a hydrogen acceptor or base.

引用

页码：3034 / 3038

页数：5

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