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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 | Mata, Jose A. | es_ES |
dc.contributor.author | Safont, Vicent S. | es_ES |
dc.date.accessioned | 2013-04-23T06:34:23Z | |
dc.date.issued | 2011 | |
dc.identifier.issn | 0276-7333 | |
dc.identifier.uri | http://hdl.handle.net/10251/28122 | |
dc.description.abstract | [EN] The catalytic hydrodefluorination (HDF) of pentafluoropyridine in the presence of arylsilanes is catalyzed by the tungsten and molybdenum(IV) cluster hydrides of formula [M3 S4 H3(dmpe)3] ¿, W-1¿for M = W and Mo-1¿for M = Mo (dmpe = 1,2-(bis)dimethylphosphinoethane). The reaction proceeds regioselectively at the 4-position under microwave radiation to yield the 2,3,5,6-tetrafluoropyridine. Catalytic activity is higher for the tungsten complexes with turnover numbers close to 100, while reactions catalyzed by molybdenum compounds are faster. A mechanism for the HDF reaction has been proposed that explains these differences based on DFT calculations. The mechanism involves partial decoordination of the diphosphine ligand that generates an empty position in the metal coordination sphere. This position together with its neighbor M-H site are used to activate the C-F bond of the pentafluoropyridine through a M-H/C-F ¿-bond metathesis mechanism involving a four-center transition state to give 2,3,5,6-tetrafluoropyridine. Subsequent coordination of the dangling diphosphine affords the para-substituted product and the [M3 S4 F3(dmpe)3] ¿ ,W-2¿ for M = W andMo-2¿ for M = Mo, cluster fluoride. The structure ofW-2¿ has been determined by single-crystal X-ray diffraction experiments. In the presence of silanes the alculated mechanism for the cluster hydride regeneration also implies three steps: (i) partial decoordination of the diphosphine, (ii) M-F/Si-H ¿-bond metathesis, and (iii) coordination of the dangling diphosphine, to afford the cluster hydride. | es_ES |
dc.description.sponsorship | The financial support of the Spanish Ministerio de Ciencia e Innovacion (Grants CTQ2008-02670), Fundacio Bancaixa-UJI (research project P1.1B2007-12), and Generalitat Valenciana (ACOMP/2010/276 and Prometeo/2009/053) is gratefully acknowledged. The authors also thank the Servei Central D'Instrumentacio Cientifica (SCIC) of the Universitat Jaume I for providing us with the mass spectrometry, NMR, and X-ray facilities. Special thanks go to Dr. Cristian Vicent for collecting diffraction data. T.B. thanks the Spanish Ministerio de Ciencia e Innovacion (MICINN) for a doctoral fellowship (FPI). | |
dc.language | Inglés | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.relation.ispartof | Organometallics | es_ES |
dc.rights | Reserva de todos los derechos | es_ES |
dc.subject | Carbon-fluorine bonds | es_ES |
dc.subject | C-F bond | es_ES |
dc.subject | Acid-assisted substitution | es_ES |
dc.subject | Potential basis-sets | es_ES |
dc.subject | Polarization functions | es_ES |
dc.subject | Coordinated hydrides | es_ES |
dc.subject | Proton-transfer | es_ES |
dc.subject | Oxidative addition | es_ES |
dc.subject | Metal-complexes | es_ES |
dc.subject | Cubane cluster | es_ES |
dc.title | Mechanism of the Catalytic Hydrodefluorination of Pentafluoropyridine by Group Six Triangular Cluster Hydrides Containing Phosphines: A Combined Experimental and Theoretical Study | es_ES |
dc.type | Artículo | es_ES |
dc.embargo.lift | 10000-01-01 | |
dc.embargo.terms | forever | es_ES |
dc.identifier.doi | 10.1021/om1009878 | |
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/UJI//P1·1B2007-12/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//ACOMP%2F2010%2F276/ | 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.; Mata, JA.; Safont, VS. (2011). Mechanism of the Catalytic Hydrodefluorination of Pentafluoropyridine by Group Six Triangular Cluster Hydrides Containing Phosphines: A Combined Experimental and Theoretical Study. Organometallics. 30(2):290-297. https://doi.org/10.1021/om1009878 | es_ES |
dc.description.accrualMethod | S | es_ES |
dc.relation.publisherversion | http://pubs.acs.org/doi/ipdf/10.1021/om1009878 | es_ES |
dc.description.upvformatpinicio | 290 | es_ES |
dc.description.upvformatpfin | 297 | es_ES |
dc.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
dc.description.volume | 30 | es_ES |
dc.description.issue | 2 | es_ES |
dc.relation.senia | 40957 | |
dc.contributor.funder | Ministerio de Ciencia e Innovación | |
dc.contributor.funder | Fundación Bancaja | |
dc.contributor.funder | Universitat Jaume I | |
dc.contributor.funder | Generalitat Valenciana |