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Title: Hydrogen generation from alcohols catalyzed by ruthenium-triphenylphosphine complexes : multiple reaction pathways
Authors: Sieffert, Nicolas
Buehl, Michael
Keywords: Homogeneous ruthenium
Alpha,beta-unsaturated aldehydes
Organometallic complexes
Noncovalent interactions
Molecular-dynamics
Olefin metathesis
Liquid water
Dehydrogenation
Coordination
Methanol
QD Chemistry
Issue Date: 16-Jun-2010
Citation: Sieffert , N & Buehl , M 2010 , ' Hydrogen generation from alcohols catalyzed by ruthenium-triphenylphosphine complexes : multiple reaction pathways ' Journal of the American Chemical Society , vol 132 , no. 23 , pp. 8056-8070 .
Abstract: We report a comprehensive density functional theory (DFT) study of the mechanism of the methanol dehydrogenation reaction catalyzed by [RuH2(H2)(PPh3)3]. Using the B97-D dispersion-corrected functional, four pathways have been fully characterized, which differ in the way the critical beta-hydrogen transfer step is brought about (e.g., by prior dissociation of one PPh3 ligand). All these pathways are found to be competitive (Delta G double dagger = 27.0-32.1 kcal/mol at 150 degrees C) and strongly interlocked. The reaction can thus follow multiple reaction channels, a feature which is expected to be at the origin of the good kinetics of this system. Our results also point to the active role of PPh3 ligands, which undergo significant conformational changes as the reaction occurs, and provide insights into the role of the base, which acts as a "co-catalyst" by facilitating proton transfers within active species. Activation barriers decrease on going from methanol to ethanol and 2-propanol substrates, in accord with experiment.
Version: Postprint
Status: Peer reviewed
URI: http://hdl.handle.net/10023/1847
DOI: http://dx.doi.org/10.1021/ja101044c
ISSN: 0002-7863
Type: Journal article
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see DOI: 10.1021/ja101044c
Appears in Collections:University of St Andrews Research
Chemistry Research



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