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The ’innocent’ role of Sc3+ on a non-heme Fe catalyst in an O2 environment

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

© Dalton Transactions, 2014, vol. 43, p. 11190-11194

Royal Society of Chemistry (RSC)

Author: Poater Teixidor, Albert
Vummaleti, Sai Vikrama Chaitanya
Cavallo, Luigi
Date: 2014
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
Format: application/pdf
ISSN: 1477-9226 (versió paper)
1477-9234 (versió electrònica)
Document access: http://hdl.handle.net/10256/10347
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MICINN/PN 2012-2015/RYC-2009-05226
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c4dt00321g
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Dalton Transactions, 2014, vol. 43, p. 11190-11194
Rights: Tots els drets reservats
Subject: Catalitzadors
Catalysts
Funcional de densitat, Teoria del
Density functionals
Title: The ’innocent’ role of Sc3+ on a non-heme Fe catalyst in an O2 environment
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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