The study of high-valent nickel complexes has attracted the attention of the bioinorganic chemistry community to provide models of nickel-containing enzymes that catalyze redox processes. Moreover, high-valent nickel-oxygen species have been frequently postulated as key reaction intermediates in the catalytic cycle of oxidation reactions. However, only a handful of such species have been properly trapped and characterized. Herein, we describe the preparation of two highly reactive high-valent nickel-oxygen compounds, namely nickel(III)-oxyl and nickel(III)-OCl radical, that have been spectroscopically trapped by reaction of a nickel(II) precursor with HmCPBA and NaOCl, respectively. The nature of both species could be unequivocally established by spectroscopic and theoretical methods. Moreover, these two species were able to oxidize organic substrates (C-H bonds, C-C double bonds and sulfides) at much faster rates compared to the previously reported well-defined Ni-oxygen species. Results disclosed here demonstrate the viability of high-valent nickel-oxygen species in oxidation reactions and their potential use as catalysts.

Spectroscopic studies and oxidizing reactivity of two high-valent nickel-oxygen species

253rd National Meeting (2017)

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