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dc.contributor.authorStylianou, M.en
dc.contributor.authorDrouza, C.en
dc.contributor.authorGiapintzakis, Johnen
dc.contributor.authorAthanasopoulos, G. I.en
dc.contributor.authorKeramidas, A. D.en
dc.creatorStylianou, M.en
dc.creatorDrouza, C.en
dc.creatorGiapintzakis, Johnen
dc.creatorAthanasopoulos, G. I.en
dc.creatorKeramidas, A. D.en
dc.date.accessioned2019-05-06T12:24:43Z
dc.date.available2019-05-06T12:24:43Z
dc.date.issued2015
dc.identifier.urihttp://gnosis.library.ucy.ac.cy/handle/7/48883
dc.description.abstractThe reaction of 2,5-bis[N,N′-bis(2-pyridyl-aminomethyl)aminomethyl]-p-hydroquinone (H2bpymah) with VO2+ salts in acetonitrile or water at a low pH (2.2-3.5) results in the isolation of [VIV(O)(Cl)2(μ-bpymah)], the p-semiquinonate complex [VIV(O)(Cl)2(μ-bpymas)](OH), the cyclic mixed-valent hexanuclear compound [VV(O)(μ-O)VIV(O)(μ-bpymah)]3, and [(VVO2)2(μ-bpymah)]. [VIV(O)(Cl)2(μ-bpymas)](OH) is an intermediate of the radical-mediated oxidation of [VIV(O)(Cl)2(μ-bpymah)] from O2. At lower pH values (2.2), a reversible intramolecular electron transfer from the metal to the ligand of [VIV(O)(Cl)2(μ-bpymas)](OH) is induced with the concurrent substitution of chlorine atoms by the oxygen-bridging atoms, resulting in the formation of [VV(O)(μ-O)VIV(O)(μ-bpymah)]3. The metal complexes were fully characterized by X-ray crystallography, infrared (IR) spectroscopy, and magnetic measurements in the solid state, as well as by conductivity measurements, UV-vis spectroscopy, and electrochemical measurements in solution. The oxidation states of the metal ions and ligands were determined by the crystallographic data. The [VIV(O)(Cl)2(μ-bpymah)]-[VIV(O)(Cl)2(μ-bpymas)](OH) redox process is electrochemically reversible. The VIV ion in the semiquinonate compound exhibits a surprisingly low oxophilicity, resulting in the stabilization of OH- counterions at acidic pH values. An investigation of the mechanism of this reaction reveals that these complexes induce the reduction of O2 to H2O2, mimicking the activity of enzymes incorporating two redox-active centers (metal-organic) in the active site. © 2015 American Chemical Society.en
dc.language.isoengen
dc.sourceInorganic chemistryen
dc.subjectModelsen
dc.subjectMolecularen
dc.subjectchemistryen
dc.subjectchemical structureen
dc.subjectoxidation reduction reactionen
dc.subjectOxidation-Reductionen
dc.subjectoxygenen
dc.subjectLigandsen
dc.subjectliganden
dc.subjectwateren
dc.subjectvanadiumen
dc.subjectpyridine derivativeen
dc.subjectPyridinesen
dc.subjectMolecular Conformationen
dc.subjectconformationen
dc.subjectCoordination Complexesen
dc.subjectcoordination compounden
dc.subjectelectrochemistryen
dc.subjectfree radicalen
dc.subjectFree Radicalsen
dc.subjecthydroquinoneen
dc.subjecthydroquinone derivativeen
dc.subjectHydroquinonesen
dc.subjectpyridineen
dc.titleAerial Oxidation of a VIV-Iminopyridine Hydroquinonate Complex: A Trap for the VIV-Semiquinonate Radical Intermediateen
dc.typeinfo:eu-repo/semantics/article
dc.identifier.doi10.1021/acs.inorgchem.5b00571
dc.description.volume54
dc.description.startingpage7218
dc.description.endingpage7229
dc.author.facultyΠολυτεχνική Σχολή / Faculty of Engineering
dc.author.departmentΤμήμα Μηχανικών Μηχανολογίας και Κατασκευαστικής / Department of Mechanical and Manufacturing Engineering
dc.type.uhtypeArticleen
dc.contributor.orcidGiapintzakis, John [0000-0002-7277-2662]
dc.description.totalnumpages7218-7229


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