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dc.contributor.authorSieffert, Nicolas
dc.contributor.authorBuehl, Michael
dc.identifier.citationSieffert , 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 .
dc.identifier.otherPURE: 5310590
dc.identifier.otherPURE UUID: 691040d9-12b6-41ec-99f8-ad74806bdf35
dc.identifier.otherWOS: 000278717700053
dc.identifier.otherScopus: 77953309840
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131810
dc.description.abstractWe 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.
dc.relation.ispartofJournal of the American Chemical Societyen
dc.rightsThis 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/ja101044cen
dc.subjectHomogeneous rutheniumen
dc.subjectAlpha,beta-unsaturated aldehydesen
dc.subjectOrganometallic complexesen
dc.subjectNoncovalent interactionsen
dc.subjectOlefin metathesisen
dc.subjectLiquid wateren
dc.subjectQD Chemistryen
dc.titleHydrogen generation from alcohols catalyzed by ruthenium-triphenylphosphine complexes : multiple reaction pathwaysen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.description.statusPeer revieweden

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