{ "dc.contributor.author": "Poater Teixidor, Albert" , "dc.contributor.author": "Vummaleti, Sai Vikrama Chaitanya" , "dc.contributor.author": "Cavallo, Luigi" , "dc.date.accessioned": "2015-05-05T06:25:06Z" , "dc.date.available": "2015-05-05T06:25:06Z" , "dc.date.issued": "2014" , "dc.identifier.issn": "1477-9226 (versió paper)" , "dc.identifier.issn": "1477-9234 (versió electrònica)" , "dc.identifier.uri": "http://hdl.handle.net/10256/10347" , "dc.description.abstract": "Density functional theory calculations have been used to investigate the reaction mechanism proposed for the formation of an oxoiron(iv) complex [Fe IV(TMC)O]2+ (P) (TMC = 1,4,8,11-tetramethylcyclam) starting from a non-heme reactant complex [FeII(TMC)]2+ (R) and O2 in the presence of acid H+ and reductant BPh4 -. We also addressed the possible role of redox-inactive Sc3+ as a replacement for H+ acid in this reaction to trigger the formation of P. Our computational results substantially confirm the proposed mechanism and, more importantly, support that Sc 3+ could trigger the O2 activation, mainly dictated by the availability of two electrons from BPh4 -, by forming a thermodynamically stable Sc3+-peroxo-Fe3+ core that facilitates O-O bond cleavage to generate P by reducing the energy barrier. These insights may pave the way to improve the catalytic reactivity of metal-oxo complexes in O2 activation at non-heme centers" , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "eng" , "dc.publisher": "Royal Society of Chemistry (RSC)" , "dc.relation": "MICINN/PN 2012-2015/RYC-2009-05226" , "dc.relation.isformatof": "Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c4dt00321g" , "dc.relation.ispartof": "© Dalton Transactions, 2014, vol. 43, p. 11190-11194" , "dc.relation.ispartofseries": "Articles publicats (D-Q)" , "dc.rights": "Tots els drets reservats" , "dc.subject": "Catalitzadors" , "dc.subject": "Catalysts" , "dc.subject": "Funcional de densitat, Teoria del" , "dc.subject": "Density functionals" , "dc.title": "The 'innocent' role of Sc3+ on a non-heme Fe catalyst in an O2 environment" , "dc.type": "info:eu-repo/semantics/article" , "dc.rights.accessRights": "info:eu-repo/semantics/embargoedAccess" , "dc.embargo.terms": "Cap" , "dc.relation.projectID": "info:eu-repo/grantAgreement/EC/FP7/293900" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" , "dc.identifier.doi": "http://dx.doi.org/10.1039/c4dt00321g" , "dc.identifier.idgrec": "022449" , "dc.contributor.funder": "Ministerio de Ciencia e Innovación (Espanya)" }