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

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Puri, Mayank
orcId Company Casadevall, Anna​ researcherId Company Casadevall, Anna​ scopusId Company Casadevall, Anna​ ​
Company Casadevall, Anna
orcId Sabeña Vila, Gerard​ ​ ​ ​
Sabeña Vila, Gerard
orcId Costas Salgueiro, Miquel​ researcherId Costas Salgueiro, Miquel​ scopusId Costas Salgueiro, Miquel​ ​
Costas Salgueiro, Miquel
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Que, Lawrence
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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 ​
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