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
收藏
页码：12229 / 12232
页数：4
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