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Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism

We report on oxygen atom exchange (OAE) reactions between H218O and non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands that proceed by a common mechanism within two kinetic regimes. One regime exhibits a linear [H218O] dependence on the OAE rate and a small H/D KIE, which mainly involves the binding of H218O to the FeiV(O) center, while the second regime exhibits OAE rates independent of [H218O] and significantly larger H/D KIEs that suggest rate determining proton transfer

The work in Girona was supported by the European Commission (2011-CIG-303522 to A.C. and ERC-2009-StG-239910 to M.C.), the Spanish Ministry of Science (CTQ2015-70795-P to M.C. and CTQ2013-43012-P to A.C.), and Generalitat de Catalunya (2014 SGR 862 and ICREA Academia Award to M.C.)

info:eu-repo/grantAgreement/MINECO//CTQ2015-70795-P/ES/GENERACION Y CARACTERIZACION DE ESPECIES DE HIERRO Y MANGANESO EN ALTOS ESTADOS DE OXIDACION, Y SU USO EN CATALISIS ASIMETRICA/

American Chemical Society (ACS)

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Puri, Mayank
Company Casadevall, Anna
Sabeña Vila, Gerard
Costas Salgueiro, Miquel
Que, Lawrence
Abstract: We report on oxygen atom exchange (OAE) reactions between H218O and non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands that proceed by a common mechanism within two kinetic regimes. One regime exhibits a linear [H218O] dependence on the OAE rate and a small H/D KIE, which mainly involves the binding of H218O to the FeiV(O) center, while the second regime exhibits OAE rates independent of [H218O] and significantly larger H/D KIEs that suggest rate determining proton transfer
The work in Girona was supported by the European Commission (2011-CIG-303522 to A.C. and ERC-2009-StG-239910 to M.C.), the Spanish Ministry of Science (CTQ2015-70795-P to M.C. and CTQ2013-43012-P to A.C.), and Generalitat de Catalunya (2014 SGR 862 and ICREA Academia Award to M.C.)
Format: application/pdf
Document access: http://hdl.handle.net/10256/13162
Language: eng
Publisher: American Chemical Society (ACS)
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.6b00023
info:eu-repo/semantics/altIdentifier/issn/0020-1669
info:eu-repo/semantics/altIdentifier/eissn/1520-510X
info:eu-repo/grantAgreement/MINECO//CTQ2013-43012-P/ES/INVESTIGACIONES MECANISTICAS PARA SINTESIS ORGANICA SOSTENIBLE VIA ACTIVACION DE PEQUEÑAS MOLECULAS GASEOSAS Y DE ENLACES C-H CON METALES DE LA PRIMERA SERIE DE TRANSICION/
info:eu-repo/grantAgreement/EC/FP7/303522/EU/Key insights into oxidation chemistry through synthetic systems: N2O activation with first-row transition-metals and O2 activation in heterobimetallic Fe-Ni systems/NEWOXMET
info:eu-repo/grantAgreement/EC/FP7/239910/EU/Bio-inspired Design of Catalysts for Selective Oxidations of C-H and C=C Bonds/BIDECASEOX
Is part of: info:eu-repo/grantAgreement/MINECO//CTQ2015-70795-P/ES/GENERACION Y CARACTERIZACION DE ESPECIES DE HIERRO Y MANGANESO EN ALTOS ESTADOS DE OXIDACION, Y SU USO EN CATALISIS ASIMETRICA/
Rights: Tots els drets reservats
Subject: Reaccions químiques
Chemical reactions
Protons -- Reaccions de transferència
Proton transfer reactions
Title: Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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