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American Chemical Society, Journal of the American Chemical Society, 50(133), p. 20088-20091, 2011

DOI: 10.1021/ja208523u

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A Highly Reactive Mononuclear Non-Heme Manganese(IV)-Oxo Complex That Can Activate the Strong C-H Bonds of Alkanes

This paper is available in a repository.
This paper is available in a repository.

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Abstract

A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of -4.4 in the oxidation of para-substituted thioanisoles.