Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(III)-Hydroperoxo Complex
- Title
- Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(III)-Hydroperoxo Complex
- Author(s)
- So, Hee ; Park, Young Jun ; Cho, Kyung-Bin ; Lee, Yong-Min ; Seo, Mi Sook ; Cho, Jaeheung ; Sarangi, Ritimukta ; Nam, Wonwoo
- Issued Date
- 2014-09-03
- Citation
- Journal of the American Chemical Society, v.136, no.35, pp.12229 - 12232
- Type
- Article
- Keywords
- SUPEROXIDE DISMUTASES ; HIGH-SPIN ; MANGANESE(III) COMPLEX ; ELECTRONIC-STRUCTURES ; ATOM-TRANSFER ; PEROXO ; IRON ; MECHANISMS ; LIGANDS ; BEARING
- ISSN
- 0002-7863
- 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 MnIII-hydroperoxo 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 MnIII-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. © 2014 American Chemical Society.
- Publisher
- American Chemical Society
- Files in This Item:
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- Appears in Collections:
- Department of Physics and Chemistry Biomimetic Materials Laboratory 1. Journal Articles
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