Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(III)-Hydroperoxo Complex

被引：58

作者：

So, Hee ^{[1
]}

Park, Young Jun ^{[1
]}

Cho, Kyung-Bin ^{[1
]}

Lee, Yong-Min ^{[1
]}

Seo, Mi Sook ^{[1
]}

Cho, Jaeheung ^{[2
]}

Sarangi, Ritimukta ^{[3
]}

Nam, Wonwoo ^{[1
]}

机构：

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

[2] DGIST, Dept Emerging Mat Sci, Taegu 711873, South Korea

[3] Stanford Univ, SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 35期

基金：

美国国家卫生研究院;

关键词：

SUPEROXIDE DISMUTASES; HIGH-SPIN; MANGANESE(III) COMPLEX; ELECTRONIC-STRUCTURES; ATOM-TRANSFER; PEROXO; IRON; MECHANISMS; LIGANDS; BEARING;

D O I：

10.1021/ja506275q

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn-III(TMC)(OOH)(2+). The Mn-III-mhydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the binding of a hydroperoxide ligand in an end-on fashion. The Mn-III-hydroperoxo species is a competent oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of sulfides. The electrophilic character of the Mn-III-hydroperoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles.

引用

页码：12229 / 12232

页数：4

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