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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.)

© Inorganic Chemistry, 2016, vol. 55, núm. 12, p. 5818-5827

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
Date: 2016 June 8
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
Citation: 025752
ISSN: 0020-1669 (versió paper)
1520-510X (versió electrònica)
Document access: http://hdl.handle.net/10256/13162
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MINECO/PE 2016-2018/CTQ2015-70795-P
MINECO/PE 2014-2016/CTQ2013-43012-P
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/acs.inorgchem.6b00023
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/303522
info:eu-repo/grantAgreement/EC/FP7/239910
Is part of: © Inorganic Chemistry, 2016, vol. 55, núm. 12, p. 5818-5827
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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