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dc.contributor.author | Beltran, Tomas F. | es_ES |
dc.contributor.author | Feliz Rodriguez, Marta | es_ES |
dc.contributor.author | Llusar, Rosa | es_ES |
dc.contributor.author | Safont, Vicent S. | es_ES |
dc.contributor.author | Vicent, Cristian | es_ES |
dc.date.accessioned | 2016-05-16T07:23:28Z | |
dc.date.available | 2016-05-16T07:23:28Z | |
dc.date.issued | 2011-11-22 | |
dc.identifier.issn | 0920-5861 | |
dc.identifier.uri | http://hdl.handle.net/10251/64097 | |
dc.description.abstract | [EN] Collision induced dissociation experiments of the alkoxo [W3S4(dmpe)(2)(O)(OCH2CH3)](+) tungsten (IV) cation reveal that aldehyde elimination is the dominant reaction pathway. Complementary deuterium labelling experiments give support to a hydrogen transfer mechanism, where the hydrogen atom exclusively originates from the alpha-position of the alkoxo ligand. On the basis of DFT calculations, two competitive mechanisms are proposed: one of them involving a proton transfer from the alpha-position of the alkoxo ligand to an oxygen atom of the vicinal W=O group; the other corresponding to a hydride transfer mechanism from the alpha-position of the alkoxo ligand to the geminate tungsten center. The calculated energy profiles show that the former is thermodynamically favoured and the second is kinetically favoured, with small energy differences between the two reaction paths; in consequence, both mechanisms compete under our experimental conditions. The proton transfer mechanism occurs through a seven-membered transition state structure while hydride transfer takes place through a four-center structure defined by the metal and the oxygen, carbon and hydrogen atoms of the ethoxo group. (C) 2011 Elsevier B. V. All rights reserved. | es_ES |
dc.description.sponsorship | The financial support of the Spanish Ministerio de Ciencia e Innovacion (research projects CTQ2008-02670 and CTQ2009-14541-C02-01), Fundacio Bancaixa-UJI (P1.1B2008-37 and P1.1B2010-46), and Generalitat Valenciana (ACOMP/2011/037) and Prometeo/2009/053) is gratefully acknowledged. The authors also thank the Servei Central d'Instrumentacio Cientifica (SCIC) and the Servei d'Informatica of the Universitat Jaume I for providing us with spectrometric facilities, and with computing time. T. F. B. thanks the Spanish Ministerio de Ciencia e Innovacion (MICINN) for a doctoral fellowship (FPI). | |
dc.language | Inglés | es_ES |
dc.publisher | Elsevier | es_ES |
dc.relation.ispartof | Catalysis Today | es_ES |
dc.rights | Reserva de todos los derechos | es_ES |
dc.subject | Tungsten clusters | es_ES |
dc.subject | Alkoxo ligands | es_ES |
dc.subject | ESI | es_ES |
dc.subject | CID | es_ES |
dc.subject | Ion-molecule reactions | es_ES |
dc.subject | DFT calculations | es_ES |
dc.title | Mechanism of the Catalytic Gas-Phase Aldehyde Production from Trinuclear W3S4 Complexes Bearing W-OEt groups | es_ES |
dc.type | Artículo | es_ES |
dc.identifier.doi | 10.1016/j.cattod.2011.05.017 | |
dc.relation.projectID | info:eu-repo/grantAgreement/MICINN//CTQ2008-02670/ES/NUEVOS ASPECTOS SOBRE LA QUIMICA DE LOS CALCOGENUROS CLUSTER DE METALES DE TRANSICION DIRIGIDOS A SUS APLICACIONES EN CATALISIS Y ELECTRONICA MOLECULAR/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/MICINN//CTQ2009-14541-C02-01/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/UJI//P1·1B2008-37/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/UJI//P1·1B2010-46/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//ACOMP%2F2011%2F037/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//PROMETEO09%2F2009%2F053/ES/Química teórica y computacional de sistemas biológicos, sólidos y de materiales moleculares (Quitecobismm)/ | es_ES |
dc.rights.accessRights | Cerrado | es_ES |
dc.contributor.affiliation | Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química | es_ES |
dc.description.bibliographicCitation | Beltran, TF.; Feliz Rodriguez, M.; Llusar, R.; Safont, VS.; Vicent, C. (2011). Mechanism of the Catalytic Gas-Phase Aldehyde Production from Trinuclear W3S4 Complexes Bearing W-OEt groups. Catalysis Today. 177(1):72-78. https://doi.org/10.1016/j.cattod.2011.05.017 | es_ES |
dc.description.accrualMethod | S | es_ES |
dc.relation.publisherversion | http://dx.doi.org/10.1016/j.cattod.2011.05.017 | es_ES |
dc.description.upvformatpinicio | 72 | es_ES |
dc.description.upvformatpfin | 78 | es_ES |
dc.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
dc.description.volume | 177 | es_ES |
dc.description.issue | 1 | es_ES |
dc.relation.senia | 212809 | es_ES |
dc.contributor.funder | Ministerio de Ciencia e Innovación | |
dc.contributor.funder | Fundación Bancaja | |
dc.contributor.funder | Universitat Jaume I | |
dc.contributor.funder | Generalitat Valenciana |