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dc.contributor.authorSieffert, Nicolas
dc.contributor.authorReocreux, Romain
dc.contributor.authorLorusso, Patrizia
dc.contributor.authorCole-Hamilton, David J.
dc.contributor.authorBuehl, Michael
dc.identifier.citationSieffert , N , Reocreux , R , Lorusso , P , Cole-Hamilton , D J & Buehl , M 2014 , ' On the importance of decarbonylation as a side-reaction in the ruthenium-catalysed dehydrogenation of alcohols : a combined experimental and density functional study ' , Chemistry - A European Journal , vol. 20 , no. 14 , pp. 4141-4155 .
dc.identifier.otherPURE: 159998693
dc.identifier.otherPURE UUID: 3bf5f019-e5ea-45d2-abe0-006e6fe46082
dc.identifier.otherWOS: 000333447200036
dc.identifier.otherScopus: 84897912386
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131766
dc.identifier.otherWOS: 000333447200036
dc.description.abstractWe report a density functional study (B97-D2 level) of the mechanism(s) operating in the alcohol decarbonylation that occurs as an important side-reaction during dehydrogenation catalysed by [RuH2(H2)(PPh3)3]. By using MeOH as the substrate, three distinct pathways have been fully characterised involving either neutral tris- or bis-phosphines or anionic bis-phosphine complexes after deprotonation. α-Agostic formaldehyde and formyl complexes are key intermediates, and the computed rate-limiting barriers are similar between the various decarbonylation and dehydrogenation paths. The key steps have also been studied for reactions involving EtOH and iPrOH as substrates, rationalising the known resistance of the latter towards decarbonylation. Kinetic isotope effects (KIEs) were predicted computationally for all pathways and studied experimentally for one specific decarbonylation path designed to start from [RuH(OCH3)(PPh3)3]. From the good agreement between computed and experimental KIEs (observed kH/kD=4), the rate-limiting step for methanol decarbonylation has been ascribed to the formation of the first agostic intermediate from a transient formaldehyde complex.
dc.relation.ispartofChemistry - A European Journalen
dc.rightsThis is the accepted version of the following article: Sieffert, N., Réocreux, R., Lorusso, P., Cole-Hamilton, D. J. and Bühl, M. (2014), On the Importance of Decarbonylation as a Side-Reaction in the Ruthenium-Catalysed Dehydrogenation of Alcohols: A Combined Experimental and Density Functional Study. Chem. Eur. J., 20: 4141–4155., which has been published in final form at
dc.subjectDensity functional calculationsen
dc.subjectIsotope effectsen
dc.subjectReaction mechanismsen
dc.subjectFormic-acid decompositionen
dc.subjectEfficient hydrogen-productionen
dc.subjectTransition-metal compoundsen
dc.subjectOlefin metathesisen
dc.subjectHighly efficienten
dc.subjectNoncovalent interactionsen
dc.subjectAgostic interactionsen
dc.subjectQD Chemistryen
dc.titleOn the importance of decarbonylation as a side-reaction in the ruthenium-catalysed dehydrogenation of alcohols : a combined experimental and density functional studyen
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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