Theoretical investigation of the selective C=C hydrogenation of unsaturated aldehydes catalyzed by [{RuCl<inf>2</inf>(mtppms)<inf>2</inf>}<inf>2</inf>] in acidic media

Gábor Kovács, Gregor Ujaque, Agustí Lledós, Ferenc Joó

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27 Citations (Scopus)

Abstract

Density functional theory has been applied to identify possible reaction intermediates for the catalytic C=C hydrogenation of cinnamaldehyde, which occurs in acidic aqueous solutions in the presence of water-soluble ruthenium phosphine complexes. On the basis of ONIOM calculations, two different active species and, hence, two pathways were proposed. The C=C bond hydrogenation takes place through the insertion of the terminal carbon atom into the Ru-H bond and subsequent protonation of the other carbon by hydroxonium ions present in the solution. We find that water is directly involved in several steps of the reaction, either as a protonating/deprotonating agent or as a coordinating ligand. Selectivity against C=O hydrogenation is due to the much higher barrier of either C insertion or O insertion into the Ru-H bond as compared to that of the C insertion in the case of the C=C functionality. © 2006 American Chemical Society.
Original languageEnglish
Pages (from-to)862-872
JournalOrganometallics
Volume25
Issue number4
DOIs
Publication statusPublished - 13 Feb 2006

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