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Unprecedented Reactivities of Highly Reactive Manganese(III)-Iodosylarene Porphyrins in Oxidation Reactions

Title
Unprecedented Reactivities of Highly Reactive Manganese(III)-Iodosylarene Porphyrins in Oxidation Reactions
Authors
Zhang, LinaLee, Yong-MinGuo, MianFukuzumi, ShunichiNam, Wonwoo
Ewha Authors
남원우이용민Shunichi FukuzumiMian Guo
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus
Issue Date
2020
Journal Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN
0002-7863JCR Link

1520-5126JCR Link
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol. 142, no. 47, pp. 19879 - 19884
Publisher
AMER CHEMICAL SOC
Indexed
SCIE; SCOPUS WOS
Document Type
Article
Abstract
We report that Mn(III)-iodosylarene porphyrins, [Mn-III(Porp)((ArIO)-Ar-s)](+), are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, with unprecedented reactivities, such as a low kinetic isotope effect, a saturation behavior of reaction rates, and no electronic effect of porphyrin ligands on the reactivities of [Mn-III(Porp)((ArIO)-Ar-s)](+). In oxygen atom transfer (OAT) reactions, the sulfoxidation of para-X-substituted thioanisoles by [Mn-III(Porp)((ArIO)-Ar-s)](+) affords a very unusual behavior in the Hammett plot with the saturation behavior of reaction rates and no electronic effect of porphyrin ligands on reactivities. The reactivities and mechanisms of [Mn-III(Porp)((ArIO)-Ar-s)](+) are then compared with those of the corresponding Mn-IV(Porp)(O) complex. The present study reports the first example of highly reactive Mn(III)-iodosylarene porphyrins with unprecedented reactivities in C-H bond activation and OAT reactions.
DOI
10.1021/jacs.0c10159
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자연과학대학 > 화학·나노과학전공 > Journal papers
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