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High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations of bis(n-oxo)dimanganese(IV) complexes with a binucleating o-phenylenedioxamate ligand

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High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations of bis(n-oxo)dimanganese(IV) complexes with a binucleating o-phenylenedioxamate ligand

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dc.contributor.author Ruiz-García, R. es_ES
dc.contributor.author Pardo, E. es_ES
dc.contributor.author Muñoz Roca, María Del Carmen es_ES
dc.contributor.author Cano, J. es_ES
dc.date.accessioned 2020-03-13T08:29:06Z
dc.date.available 2020-03-13T08:29:06Z
dc.date.issued 2007-01-01 es_ES
dc.identifier.issn 0020-1693 es_ES
dc.identifier.uri http://hdl.handle.net/10251/138897
dc.description.abstract [EN] Two novel bis(oxo)-bridged dinuclear manganese(IV) complexes with the binucleating ligand o-phenylenebis(oxamate) (opba), formulated as (Me4N)(4)[Mn2O2(opba)(2)] (1a) and (Me4N)(2)(Ph4P)(2)[Mn2O2(opba)(2)] (.) 8H(2)O (1b), have been synthesized and characterized structurally and magnetically. Like the parent complex (Ph4P)(4)[Mn2O2(opba)(2)] (.) 4H(2)O (1c), they possess unique Mn-2(mu-O)(2) bridging cores with two additional o-phenylenediamidate bridges which lead to exceptionally short Mn-Mn distances (2.63-2.67 angstrom) and fairly bent Mn-O-Mn angles (93.8-95.5 degrees). Complexes 1a-c show a moderate to strong antiferromagnetic coupling between the two high-spin Mn-IV ions through the bis(oxo)bis(o-phenylenediamidate) quadruple bridge (-J = 70-164 cm(-1); H = -JS(1) (.) S-2) Along this series, the -J values increase with the shortening of the Mn-Mn distance and/or the lessening of the Mn-O-Mn angle. Electronic structure calculations on model complexes reproduce the observed dependence of -J with the Mn-O-Mn angle at short intermetallic distances, and reveal that the magnetic coupling is dominated by the in-plane 3d(x2-y2) type superexchange pathway via the oxo bridges with a small but nonnegligible contribution from direct 3d(x2-y2) type Mn-Mn sigma-bond. es_ES
dc.description.sponsorship This work was supported by the Oficina de Ciencia i Tecnología de la Generalitat Valenciana (Spain) through the Plan Valenciano de Investigación Científica, Desarrollo Tecnológico e Innovación (PVIDI) (CTIDIA2002-131) and the Ministerio de Ciencia y Tecnología (MCYT) (Spain) through the Ramón y Cajal program. R.R.-G. thanks all his colleagues in the research group of Prof. José R. Pedro at the Universitat de València where he has developed the work on the biomimetic chemistry of high-valent transition metal complexes in the last years. He is specially thankful to Dr. X. Ottenwaelder (Stanford University) for very stimulating talks and unselfish help during this period. es_ES
dc.language Inglés es_ES
dc.publisher Elsevier es_ES
dc.relation GV/CTIDIA2002-131 es_ES
dc.relation.ispartof Inorganica Chimica Acta es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject Amides es_ES
dc.subject Carboxylates es_ES
dc.subject Density functional theory calculations es_ES
dc.subject Magnetic properties es_ES
dc.subject Manganese es_ES
dc.subject Photosystem II es_ES
dc.subject.classification FISICA APLICADA es_ES
dc.title High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations of bis(n-oxo)dimanganese(IV) complexes with a binucleating o-phenylenedioxamate ligand es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1016/j.ica.2006.07.064 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 Ruiz-García, R.; Pardo, E.; Muñoz Roca, MDC.; Cano, J. (2007). High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations of bis(n-oxo)dimanganese(IV) complexes with a binucleating o-phenylenedioxamate ligand. Inorganica Chimica Acta. 360(1):221-232. https://doi.org/10.1016/j.ica.2006.07.064 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion https://doi.org/10.1016/j.ica.2006.07.064 es_ES
dc.description.upvformatpinicio 221 es_ES
dc.description.upvformatpfin 232 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 360 es_ES
dc.description.issue 1 es_ES
dc.relation.pasarela S\230647 es_ES
dc.contributor.funder Generalitat Valenciana es_ES
dc.contributor.funder Ministerio de Ciencia y Tecnología es_ES


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