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

Author(s)
So, HeePark, Young JunCho, Kyung-BinLee, Yong-MinSeo, Mi SookCho, JaeheungSarangi, RitimuktaNam, Wonwoo
Issued Date
2014-09
DOI
10.1021/ja506275q
URI
https://scholarworks.unist.ac.kr/handle/201301/48119
Fulltext
https://pubs.acs.org/doi/10.1021/ja506275q
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.136, no.35, pp.12229 - 12232
Abstract
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.
Publisher
AMER CHEMICAL SOC
ISSN
0002-7863
Keyword
SUPEROXIDE DISMUTASESHIGH-SPINMANGANESE(III) COMPLEXELECTRONIC-STRUCTURESATOM-TRANSFERPEROXOIRONMECHANISMSLIGANDSBEARING

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