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

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A Highly Reactive Mononuclear Non-Heme Manganese(IV)–Oxo Complex That Can Activate the Strong C–H Bonds of Alkanes
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2011-12-21 , DOI: 10.1021/ja208523u
Xiujuan Wu ₁ , Mi Sook Seo ₁ , Katherine M. Davis ₂ , Yong-Min Lee ₁ , Junying Chen ₁ , Kyung-Bin Cho ₁ , Yulia N. Pushkar ₂ , Wonwoo Nam ₁

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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.

中文翻译：

一种高反应性单核非血红素锰 (IV)-氧杂络合物，可以激活烷烃的强 C-H 键

使用各种光谱方法合成和表征了单核非血红素锰 (IV)-氧配合物。Mn(IV)-oxo 络合物在氧化反应中表现出高反应性，例如 CH 键活化、烯烃、醇、硫化物和芳族化合物的氧化以及 N-脱烷基化。在 CH 键活化中，Mn(IV)-oxo 络合物可以激活与环己烷中的 CH 键一样强的 CH 键。有人提出，非血红素 Mn(IV)-氧配合物对 CH 键的活化不会通过氧回弹机制发生。在对位取代的苯硫醚氧化过程中，-4.4 的大负 ρ 值证明了非血红素 Mn(IV)-氧代复合物的亲电特性。

更新日期：2011-12-21

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