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

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posted on 21.12.2011, 00:00 by Xiujuan Wu, Mi Sook Seo, Katherine M. Davis, Yong-Min Lee, Junying Chen, Kyung-Bin Cho, Yulia N. Pushkar, Wonwoo Nam
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.