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

被引：183

作者：

Wu, Xiujuan ^{[2
]}

Seo, Mi Sook ^{[2
]}

Davis, Katherine M. ^{[1
]}

Lee, Yong-Min ^{[2
]}

Chen, Junying ^{[2
]}

Cho, Kyung-Bin ^{[2
]}

Pushkar, Yulia N. ^{[1
]}

Nam, Wonwoo ^{[2
]}

机构：

[1] Purdue Univ, Dept Phys, W Lafayette, IN 47907 USA

[2] Ewha Womans Univ, Dept Chem & Nano Sci, Dept Bioinspired Sci, Seoul 120750, South Korea

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 50期

基金：

美国国家科学基金会;

关键词：

HYDROGEN-ATOM TRANSFER; MANGANESE(V)-OXO PORPHYRIN COMPLEXES; HYDRIDE-TRANSFER-REACTIONS; IRON-OXO COMPLEXES; HIGH-VALENT IRON; REACTION-MECHANISMS; WATER OXIDATION; PHOTOSYSTEM-II; METAL OXO; HYDROXYLATION;

D O I：

10.1021/ja208523u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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-deallcylation. 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 p value of -4.4 in the oxidation of para-substituted thioanisoles.

引用

页码：20088 / 20091

页数：4

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