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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
Authors
So, H[So, Hee]Park, YJ[Park, Young Jun]Cho, KB[Cho, Kyung-Bin]Lee, YM[Lee, Yong-Min]Seo, MS[Seo, Mi Sook]Cho, J[Cho, Jaeheung]Sarangi, R[Sarangi, Ritimukta]Nam, W[Nam, Wonwoo]
DGIST Authors
Cho, J[Cho, Jaeheung]
Issue Date
2014-09-03
Citation
Journal of the American Chemical Society, 136(35), 12229-12232
Type
Article
Article Type
Article
Keywords
ChemistryCoordination ComplexesCoordination CompoundCyclamHeterocyclic CompoundHeterocyclic CompoundsHydrogen PeroxideLigandLigandsManganeseMethylphenylsulfideOxidantsOxidation-ReductionOxidation-Reduction ReactionOxidizing AgentSulfideSulfides
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.
URI
http://hdl.handle.net/20.500.11750/2378
DOI
10.1021/ja506275q
Publisher
American Chemical Society
Files:
There are no files associated with this item.
Collection:
Emerging Materials ScienceETC1. Journal Articles


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