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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.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.relation.projectID | info:eu-repo/grantAgreement/GVA//CTIDIA2002-131/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/MICYT//BQU2001-3017/ES/Complejos de metales de transición como catalizadores biomiméticos en síntesis orgánica: De la catálisis oxidativa a la catálisis de ácidos de Lewis/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//AVCYT 03%2F168/ | 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 |