Hydrogenation of polar bonds catalysed by ruthenium-pincer complexes

TitleHydrogenation of polar bonds catalysed by ruthenium-pincer complexes
Publication TypeJournal Article
Year of Publication2014
AuthorsBalaraman, E, Milstein, D
Secondary AuthorsBruneau, C, Dixneuf, PH
JournalRuthenium in Catalysis
Date PublishedMAR
ISBN Number978-3-319-08482-4; 978-3-319-08481-7
KeywordsAmides, Carbon dioxide, Esters, Hydrogen, Hydrogenation, Metal-ligand cooperation, Pincer complexes, ruthenium

Catalytic hydrogenation of polar bonds using molecular hydrogen is an important, atom-economical synthetic reaction. Classical reduction methods of polar bond often require reactive metal-hydride reagents in stoichiometric amount and produce copious waste. Hydrogenation of carbonyl compounds in particular provides `green' approaches to synthetically important building blocks, such as alcohols and amines. We have designed and synthesized several ruthenium-based pincer catalysts for unprecedented hydrogenation reactions including: (1) amides to alcohols and amines, (2) biomass-derived di-esters to 1,2-diols and (3) CO2 and CO derivatives to methanol. These atom-economical reactions operate under neutral, homogeneous conditions, at mild temperatures, mild hydrogen pressures, and can operate in absence of solvent with no generation of waste. The postulated mechanisms involve metal-ligand cooperation (MLC) by aromatization-dearomatization of the heteroaromatic pincer core.

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Catalysis and Inorganic Chemistry