title: Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids.
abstract: Carboxylic acids are ubiquitous in bio-renewable and petrochemical sources of carbon. Hydrogenation of carboxylic acids to yield alcohols produces water as the only byproduct, and thus represents a possible next generation, sustainable method for the production of these alternative energy carriers/platform chemicals on a large scale. Reported herein are molecular insights into cationic mononuclear ruthenium carboxylates ([Ru(OCOR)](+)) as prototypical catalysts for the hydrogenation of carboxylic acids. The substrate-derived coordinated carboxylate was found to function initially as a proton acceptor for the heterolytic cleavage of dihydrogen, and subsequently also as an acceptor for the hydride from [Ru-H](+), which was generated in the first step (self-induced catalysis). The hydrogenation proceeded selectively and at high levels of functional group tolerance, a feature that is challenging to achieve with existing heterogeneous/homogeneous catalyst systems. These fundamental insights are expected to significantly benefit the future development of metal carboxylate-catalysed hydrogenation processes of bio-renewable resources.
authors: Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.
authors: Masayuki
authors: M
authors: Naruto
authors: Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.|Institute for Advanced Research, Nagoya University, Chikusa, Nagoya 464-8601, Japan.|ACT-C, JST, Chikusa, Nagoya 464-8602, Japan.
authors: Susumu
authors: S
authors: Saito