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Structure and Reactivity of Nonporphyrinic Terminal Manganese(IV)-Hydroxide Complexes in the Oxidative Electrophilic Reaction

Title
Structure and Reactivity of Nonporphyrinic Terminal Manganese(IV)-Hydroxide Complexes in the Oxidative Electrophilic Reaction
Authors
Park, YounwooKim, SeonghanKim, KyungminShin, BongkiJang, YoungchaeCho, Kyung-BinCho, Jaeheung
DGIST Authors
Park, Younwoo; Kim, Seonghan; Kim, Kyungmin; Shin, Bongki; Jang, Youngchae; Cho, Kyung-Bin; Cho, Jaeheung
Issue Date
2022-03
Citation
Inorganic Chemistry, 61(10), 4292-4301
Type
Article
Keywords
HYDROGEN-ATOM TRANSFERH BOND OXIDATIONMANGANESE(IV) COMPLEXMETAL-OXOHYDROXIDE COMPLEXOXYGEN ACTIVATIONCRYSTAL-STRUCTUREPHOTOSYSTEM-IIBASIS-SETSLIPOXYGENASE
ISSN
0020-1669
Abstract
High-valent transition metal-hydroxide complexes have been proposed as essential intermediates in biological and synthetic catalytic reactions. In this work, we report the single-crystal X-ray structure and spectroscopic characteristics of a mononuclear nonporphyrinic MnIV-(OH) complex, [MnIV(Me3-TPADP)(OH)(OCH2CH3)]2+ (2), using various physicochemical methods. Likewise, [MnIV(Me3-TPADP)(OH)(OCH2CF3)]2+ (3), which is thermally stable at room temperature, was also synthesized and characterized spectroscopically. The MnIV-(OH) adducts are capable of performing oxidation reactions with external organic substrates such as C-H bond activation, sulfoxidation, and epoxidation. Kinetic studies, involving the Hammett correlation and kinetic isotope effect, and product analyses indicate that 2 and 3 exhibit electrophilic oxidative reactivity toward hydrocarbons. Density functional theory calculations support the assigned electronic structure and show that direct C-H bond activation of the MnIV-(OH) species is indeed possible. © 2021 American Chemical Society. All rights reserved.
URI
http://hdl.handle.net/20.500.11750/16435
DOI
10.1021/acs.inorgchem.1c03104
Publisher
American Chemical Society
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