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• W2017812773 abstract "The aqueous iron(IV) ion, Fe(IV)(aq)O(2+), generated from O(3) and Fe(aq)(2+), reacts rapidly with various oxygen atom acceptors (sulfoxides, a water-soluble triarylphosphine, and a thiolatocobalt complex). In each case, Fe(IV)(aq)O(2+) is reduced to Fe(aq)(2+), and the substrate is oxidized to a product expected for oxygen atom transfer. Competition methods were used to determine the kinetics of these reactions, some of which have rate constants in excess of 10(7) M(-1) s(-1). Oxidation of dimethyl sulfoxide (DMSO) has k = 1.26 x 10(5) M(-1) s(-1) and shows no deuterium kinetic isotope effect, k(DMSO-d(6)) = 1.23 x 10(5) M(-1) s(-1). The Fe(IV)(aq)O(2+)/sulfoxide reaction is the product-forming step in a very efficient Fe(aq)(2+)-catalyzed oxidation of sulfoxides by ozone. This catalytic cycle, combined with labeling experiments in H(2)(18)O, was used to determine the rate constant for the oxo-group exchange between Fe(IV)(aq)O(2+) and solvent water under acidic conditions, k(exch) = 1.4 x 10(3) s(-1)." @default.
• W2017812773 created "2016-06-24" @default.
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• W2017812773 date "2005-12-14" @default.
• W2017812773 modified "2023-10-14" @default.
• W2017812773 title "Aqueous Ferryl(IV) Ion: Kinetics of Oxygen Atom Transfer To Substrates and Oxo Exchange with Solvent Water" @default.
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• W2017812773 doi "https://doi.org/10.1021/ic051868z" @default.
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