Articles producció científica> Química Física i Inorgànica

Dicobalt-µ-oxo Polyoxometalate Compound, [(a2-P2W17O61Co)2O]14-: A Potent Species for Water Oxidation, C-H Bond Activation and Oxygen Transfer

  • Datos identificativos

    Identificador: PC:598
    Handle: https://hdl.handle.net/20.500.11797/PC598
    Autores:
    Barats-Damatov, D.Shimon, L.J.W.Weiner, L.Schreiber, R.E.Jiménez-Lozano, P.Poblet, J.M.de Graaf, C.Neumann, R.
    Resumen:
    10.1021/ic402962c

  • Otros:

    Autor según el artículo: Barats-Damatov, D. Shimon, L.J.W. Weiner, L. Schreiber, R.E. Jiménez-Lozano, P. Poblet, J.M. de Graaf, C. Neumann, R.
    Departamento: Química Física i Inorgànica
    Resumen: High-valent oxo compounds of transition metals are often implicated as active species in oxygenation of hydrocarbons through carbon-hydrogen bond activation or oxygen transfer and also in water oxidation. Recently, several examples of cobalt-catalyzed water oxidation have been reported, and cobalt(IV) species have been suggested as active intermediates. A reactive species, formally a dicobalt(IV)-µ-oxo polyoxometalate compound [(a2- P2W17O61Co)2O]14-, [(POMCo)2O], has now been isolated and characterized by the oxidation of a monomeric [a2-P2W17O 61CoII(H2O)]8-, [POMCo IIH2O], with ozone in water. The crystal structure shows a nearly linear Co-O-Co moiety with a Co-O bond length of ~1.77 Å. In aqueous solution [(POMCo)2O] was identified by 31P NMR, Raman, and UV-vis spectroscopy. Reactivity studies showed that [(POMCo) 2O]2O] is an active compound for the oxidation of H 2O to O2, direct oxygen transfer to water-soluble sulfoxides and phosphines, indirect epoxidation of alkenes via a Mn porphyrin, and the selective oxidation of alcohols by carbon-hydrogen bond activation. The latter appears to occur via a hydrogen atom transfer mechanism. Density functional and CASSCF calculations strongly indicate that the electronic structure of [(POMCo)2O]2O] is best defined as a compound having two cobalt(III) atoms with two oxidized oxygen atoms.
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0020-1669
    Página final: 1787
    Volumen de revista: 53
    Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
    Enlace a la fuente original: http://pubs.acs.org/doi/abs/10.1021/ic402962c
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI del artículo: 10.1021/ic402962c
    Entidad: Universitat Rovira i Virgili.
    Año de publicación de la revista: 2014
    Página inicial: 1779