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Chemistry and reactivity of mononuclear manganese oxamate complexes: Oxidative carbon-carbon bond cleavage of vic-diols by dioxygen and aldehydes catalyzed by a trans-dipyridine manganese(III) complex with a tetradentate o-phenylenedioxamate ligand

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Chemistry and reactivity of mononuclear manganese oxamate complexes: Oxidative carbon-carbon bond cleavage of vic-diols by dioxygen and aldehydes catalyzed by a trans-dipyridine manganese(III) complex with a tetradentate o-phenylenedioxamate ligand

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dc.contributor.author Barroso, S. es_ES
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 Pardo, E. es_ES
dc.contributor.author Lloret, F. es_ES
dc.contributor.author Muñoz Roca, María Del Carmen es_ES
dc.date.accessioned 2020-04-17T12:48:07Z
dc.date.available 2020-04-17T12:48:07Z
dc.date.issued 2006-01-16 es_ES
dc.identifier.issn 1381-1169 es_ES
dc.identifier.uri http://hdl.handle.net/10251/140837
dc.description.abstract [EN] Two new mononuclear octahedral manganese(III) complexes with the tetradentate equatorial ligand o-phenylenebis(oxamate) (opba) and two aquo (1a) or two pyridine (1b) axial ligands have been synthesized and characterized structurally, magnetically, and electrochemically. The cyclovoltammogram of 1a in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) shows an irreversible one-electron oxidation peak at a high anodic potential (E-ap = 1.03 V versus SCE), while that of 1b shows two well-separated one-electron oxidation peaks at moderate to high anodic potentials (E-ap = 0.92 and 1.27 V versus SCE), the first redox-wave being quasireversible in nature. The access to formally high-valent Mn-IV and Mn-V oxidation states for 1b is attributed to the stabilization effect of axial pyridine ligand coordination. Complex 1b has been used as an efficient catalyst for the aerobic oxidative cleavage of aromatic vic-diols with co-oxidation of pivalaldehyde to pivalic acid. The corresponding aldehydes or ketones are obtained in fair to good yields and moderate selectivities in acetonitrile at 40 degrees C. Under the same experimental conditions, complex la shows lower efficiencies and selectivities than 1b. The modulation of catalytic activity by the axial pyridine ligands highlights the role of oxomanganese(V) species as the putative intermediates in these C-C bond cleavage oxidation reactions. 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. SB and EP thank the Universitat de Valencia and the Ministerio de Educación, Cultura y Deporte (Spain), respectively, for grants. We are specially thankful to S. Currelli for the assistance with the electrochemical measurements. 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 C-C bond activation 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 mononuclear manganese oxamate complexes: Oxidative carbon-carbon bond cleavage of vic-diols by dioxygen and aldehydes catalyzed by a trans-dipyridine manganese(III) complex with a tetradentate o-phenylenedioxamate ligand es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1016/j.molcata.2005.08.027 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 Barroso, S.; Blay, G.; Fernández, I.; Pedro, JR.; Ruiz-García, R.; Pardo, E.; Lloret, F.... (2006). Chemistry and reactivity of mononuclear manganese oxamate complexes: Oxidative carbon-carbon bond cleavage of vic-diols by dioxygen and aldehydes catalyzed by a trans-dipyridine manganese(III) complex with a tetradentate o-phenylenedioxamate ligand. Journal of Molecular Catalysis A Chemical. 243(2):214-220. https://doi.org/10.1016/j.molcata.2005.08.027 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion https://doi.org/10.1016/j.molcata.2005.08.027 es_ES
dc.description.upvformatpinicio 214 es_ES
dc.description.upvformatpfin 220 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 243 es_ES
dc.description.issue 2 es_ES
dc.relation.pasarela S\230657 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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