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Chemistry and reactivity of dinuclear manganese oxamate complexes: Aerobic catechol oxidation catalyzed by high-valent bis(oxo)-bridged dimanganese(IV) complexes with a homologous series of binucleating 4,5-disubstituted-o-phennylenedioxamate ligands

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Chemistry and reactivity of dinuclear manganese oxamate complexes: Aerobic catechol oxidation catalyzed by high-valent bis(oxo)-bridged dimanganese(IV) complexes with a homologous series of binucleating 4,5-disubstituted-o-phennylenedioxamate ligands

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dc.contributor.author Blay, G. es_ES
dc.contributor.author Fernández, I. es_ES
dc.contributor.author Pedro, J. R. es_ES
dc.contributor.author Ruiz-García, R. es_ES
dc.contributor.author Temporal-Sánchez, T. es_ES
dc.contributor.author Pardo, E. es_ES
dc.contributor.author Lloret, F. es_ES
dc.contributor.author Muñoz Roca, María Del Carmen es_ES
dc.date.accessioned 2020-04-17T12:49:13Z
dc.date.available 2020-04-17T12:49:13Z
dc.date.issued 2006-05-02 es_ES
dc.identifier.issn 1381-1169 es_ES
dc.identifier.uri http://hdl.handle.net/10251/140873
dc.description.abstract [EN] The high-valent bis(oxo)-bridged dimanganese(IV) complexes with the series of binucleating 4.5-X-2-o-phenylenebis(oxamate) ligands (opbaX(2); X = H, Cl, Me) (1a-c) have been synthesized and characterized structurally, spectroscopically and magnetically. Complexes la-c possess unique Mn-2(mu-O)(2) core structures with two o-phenylenediamidate type additional bridges which lead to exceptionally short Mn-Mn distances (2.63-2.65 angstrom) and fairly bent Mn-O-Mn angles (94.1 degrees-94.6 degrees). The cyclovoltammograms of la-c in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) show an irreversible one-electron oxidation peak at moderately high anodic potentials (E-ap = 0.50-0.85 V versus SCE), while no reductions are observed in the potential range studied (down to -2.0 V versus SCE). These dinuclear manganese oxamate complexes are excellent catalysts for the aerobic oxidation of 3,5-di-tert-butylcatechol to the corresponding o-quinone in acetonitrile at 25 degrees C. The order of increasing catecholase activity (k(obs)) with the electron donor character of the ligand substituents as 1b (X = Cl) < 1a (X = H) < 1c (X = Me) correlates with Hammett sigma(+) values (p = -0.95). A mechanism involving initial activation of the catechol substrate by coordination to the dimetal center and subsequent oxidation to quinone by O-2 is proposed, which is consistent with the observed saturation kinetics. es_ES
dc.description.sponsorship This work was supported by the Ministerio de Ciencia y Tecnología (Spain) (Project BQU2001-3017) and the Ramon y Cajal program. Further support from the Generalitat Valenciana (Spain) (Project CTIDIA2002-131 and AVCYT Grupos 03/168) is also acknowledged. E. P. thanks the Ministerio de Educación, Cultura y Deporte (Spain) for a grant. es_ES
dc.language Inglés es_ES
dc.publisher Elsevier es_ES
dc.relation GV/CTIDIA2002-131 es_ES
dc.relation MCYT/BQU2001-3017 es_ES
dc.relation GV/AVCYT 03/168 es_ES
dc.relation.ispartof Journal of Molecular Catalysis A Chemical es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject Catalysis es_ES
dc.subject Catechols es_ES
dc.subject Manganese es_ES
dc.subject O-O Bond activation es_ES
dc.subject Oxidations es_ES
dc.subject Redox properties es_ES
dc.subject.classification FISICA APLICADA es_ES
dc.title Chemistry and reactivity of dinuclear manganese oxamate complexes: Aerobic catechol oxidation catalyzed by high-valent bis(oxo)-bridged dimanganese(IV) complexes with a homologous series of binucleating 4,5-disubstituted-o-phennylenedioxamate ligands es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1016/j.molcata.2006.01.021 es_ES
dc.rights.accessRights Cerrado es_ES
dc.contributor.affiliation Universitat Politècnica de València. Departamento de Física Aplicada - Departament de Física Aplicada es_ES
dc.description.bibliographicCitation Blay, G.; Fernández, I.; Pedro, JR.; Ruiz-García, R.; Temporal-Sánchez, T.; Pardo, E.; Lloret, F.... (2006). Chemistry and reactivity of dinuclear manganese oxamate complexes: Aerobic catechol oxidation catalyzed by high-valent bis(oxo)-bridged dimanganese(IV) complexes with a homologous series of binucleating 4,5-disubstituted-o-phennylenedioxamate ligands. Journal of Molecular Catalysis A Chemical. 250(1-2):20-26. https://doi.org/10.1016/j.molcata.2006.01.021 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion https://doi.org/10.1016/j.molcata.2006.01.021 es_ES
dc.description.upvformatpinicio 20 es_ES
dc.description.upvformatpfin 26 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 250 es_ES
dc.description.issue 1-2 es_ES
dc.relation.pasarela S\230656 es_ES
dc.contributor.funder Generalitat Valenciana es_ES
dc.contributor.funder Ministerio de Ciencia y Tecnología es_ES
dc.contributor.funder Ministerio de Educación, Cultura y Deporte es_ES


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