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Structure and Reactivity of a Mononuclear Nonheme Manganese(III)-Iodosylarene Complex

Title
Structure and Reactivity of a Mononuclear Nonheme Manganese(III)-Iodosylarene Complex
Authors
Jeong, DonghyunOhta, TakehiroCho, Jaeheung
DGIST Authors
Cho, Jaeheung
Issue Date
2018-11
Citation
Journal of the American Chemical Society, 140(47), 16037-16041
Type
Article
Article Type
Article
Keyword
MULTIPLE ACTIVE OXIDANTS; DIOXYGEN ACTIVATION; HYPERVALENT IODINE; OXYGEN-TRANSFER; ATOM TRANSFER; IRON; EPOXIDATION; MANGANESE; WATER; IRON(III)
ISSN
0002-7863
Abstract
Transition metal-iodosylarene complexes have been proposed to be key intermediates in the catalytic cycles of metal catalysts with iodosylarene. We report the first X-ray crystal structure and spectroscopic characterization of a mononuclear nonheme manganese(III)-iodosylarene complex with a tetradentate macrocyclic ligand, [MnIII(TBDAP)(OIPh)(OH)]2+ (2). The manganese(III)-iodosylarene complex is capable of conducting various oxidation reactions with organic substrates, such as C-H bond activation, sulfoxidation and epoxidation. Kinetic studies including isotope labeling experiments and Hammett correlation demonstrate the electrophilic character on the Mn-iodosylarene adduct. This novel intermediate would be prominently valuable for expanding the chemistry of transition metal catalysts. Copyright © 2018 American Chemical Society.
URI
http://hdl.handle.net/20.500.11750/9494
DOI
10.1021/jacs.8b10244
Publisher
American Chemical Society
Related Researcher
  • Author Cho, Jaeheung Biomimetic Materials Laboratory
  • Research Interests Biomimetics; Metalloenzymes; Nitric Oxide Suppliers in Brain; Biomimetic Materials in Life
Files:
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Collection:
Department of Emerging Materials ScienceBiomimetic Materials Laboratory1. Journal Articles


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