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Ministerio de Ciencia e Innovación (Espanya) | |
Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya Cavallo, Luigi |
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2014 | |
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 | |
application/pdf | |
http://hdl.handle.net/10256/10347 | |
eng | |
Royal Society of Chemistry (RSC) | |
info:eu-repo/semantics/altIdentifier/doi/10.1039/c4dt00321g info:eu-repo/semantics/altIdentifier/issn/1477-9226 info:eu-repo/semantics/altIdentifier/eissn/1477-9234 info:eu-repo/grantAgreement/MICINN//RYC-2009-05226/ES/RYC-2009-05226/ info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG |
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Tots els drets reservats | |
Catalitzadors
Catalysts Funcional de densitat, Teoria del Density functionals |
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The ’innocent’ role of Sc3+ on a non-heme Fe catalyst in an O2 environment | |
info:eu-repo/semantics/article | |
DUGiDocs |