Abstract

AbstractNaphthalene oxidation with metal–oxygen intermediates is a difficult reaction in environmental and biological chemistry. Herein, we report that a MnIV bis(hydroxo) complex, which was fully characterized by various physicochemical methods, such as ESI‐MS, UV/Vis, and EPR analysis, X‐ray diffraction, and XAS, can be employed for the oxidation of naphthalene in the presence of acid to afford 1,4‐naphthoquinone. Redox titration of the MnIV bis(hydroxo) complex gave a one‐electron reduction potential of 1.09 V, which is the most positive potential for all reported nonheme MnIV bis(hydroxo) species as well as MnIV oxo analogues. Kinetic studies, including kinetic isotope effect analysis, suggest that the naphthalene oxidation occurs through a rate‐determining electron transfer process.

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