The active role of the water solvent in the regioselective C=O hydrogenation of unsaturated aldehydes by [RuH2(mtppms)x] in basic media

Andrea Rossin, Gabor Kovács, Gregori Ujaque, Agustí Lledós, Ferenc Joó

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Abstract

The regioselective hydrogenation of cinnamaldehyde in basic aqueous media catalyzed by [RuH2(mtppms)x [x -3,4; mtppms = meta-sulfonatophenyl-diphenylphosphine] is analyzed by means of theoretical calculations. The water solvent is modeled by the inclusion of a (H 2O)3 cluster in addition to a continuum model. Two Ru complexes are evaluated as active species for the reduction process: the major identified species [RuH2P4] and the related phosphine dissociated complex [RuH2P4]. Several reaction mechanisms are computationally evaluated, and their analysis suggests that the reaction takes place in several steps. The first hydrogenation process takes place by means of a hydrogen transfer from the metal catalyst, whereas the second hydrogenation process is performed by a water solvent molecule. This mechanism can account for the selectivity of the C=O versus C=C double bond reduction experimentally observed under basic reaction conditions and can be directly related to the mechanism found in acidic media, where the opposite regioselectivity (C=C vs C=O) is observed. © 2006 American Chemical Society.
Original languageEnglish
Pages (from-to)5010-5023
JournalOrganometallics
Volume25
Issue number21
DOIs
Publication statusPublished - 9 Oct 2006

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