Hydroxycarbonyl complexes as key intermediates in the base-assisted reduction of ruthenium carbonyls?

Dalton Transactions Pub Date: 2010-09-28 DOI: 10.1039/C0DT00679C

Abstract

Since the recognition of metal-hydroxycarbonyl (or, metallacarboxylic acid) as a key intermediate in water gas shift (WGS) catalysis, numerous metal complexes incorporating hydroxycarbonyl ligands have been synthesized. In this Perspective, a brief account on the chemistry of metallacarboxylic acid and metallacarboxylate is presented. Special emphasis is placed on the hydroxycarbonyl-bridged dinuclear compounds. The relevance of hydroxycarbonyl complexes in the base-assisted reduction of ruthenium carbonyls is investigated. In particular, Lavigne's synthesis of Roper's catalyst Ru(CO)2(PPh3)3, triruthenium dodecacarbonyl Ru3(CO)12, and Bera's mechanistic investigation on the preparation of the metal–metal singly bonded diruthenim(I) complex [Ru2(CO)4(CH3CN)6]2+ are described in detail. These reactions involve the decarboxylation of a “[Rum(COOH)n]” species, followed by the reductive elimination of HX (X = H, Cl or OH), steps akin to WGS catalysis. The prospect of hydroxycarbonyl chemistry in the development of bimetallic catalysis is examined.

Graphical abstract: Hydroxycarbonyl complexes as key intermediates in the base-assisted reduction of ruthenium carbonyls
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