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dc.contributor.authorPoater, Albert
dc.contributor.authorChaitanya Vummaleti, Sai Vikrama
dc.contributor.authorCavallo, Luigi
dc.date.accessioned2015-08-03T11:43:29Z
dc.date.available2015-08-03T11:43:29Z
dc.date.issued2014
dc.identifier.issn14779226
dc.identifier.doi10.1039/c4dt00321g
dc.identifier.urihttp://hdl.handle.net/10754/563221
dc.description.abstractDensity 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. This journal is © the Partner Organisations 2014.
dc.description.sponsorshipA.P. thanks the Spanish MIClNN for a Ramon y Cajal contract (RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900). We thank Prof. Lawrence Que Jr for helpful comments.
dc.publisherRoyal Society of Chemistry (RSC)
dc.titleThe "innocent" role of Sc3+ on a non-heme Fe catalyst in an O2 environment
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.contributor.departmentChemical Science Program
dc.identifier.journalDalton Transactions
dc.contributor.institutionInstitut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona Campus de Montilivi, E-17071 Girona Catalonia, Spain
dc.contributor.institutionCatalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, E-17003 Girona, Spain
kaust.personCavallo, Luigi
kaust.personPoater, Albert
kaust.personChaitanya Vummaleti, Sai Vikrama


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