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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.)

American Chemical Society (ACS)

Director: Ministerio de Economía y Competitividad (Espanya)
Autor: Puri, Mayank
Company Casadevall, Anna
Sabeña, Gerard
Costas Salgueiro, Miquel
Que, Lawrence
Resum: 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.)
Accés al document: http://hdl.handle.net/2072/298552
Llenguatge: eng
Editor: American Chemical Society (ACS)
Drets: Tots els drets reservats
Matèria: Reaccions químiques
Chemical reactions
Protons -- Reaccions de transferència
Proton transfer reactions
Títol: Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism
Tipus: info:eu-repo/semantics/article
Repositori: Recercat

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