Unprecedented Reactivities of Highly Reactive Manganese(III)-Iodosylarene Porphyrins in Oxidation Reactions
- 주제(기타) Chemistry, Multidisciplinary
- 설명문(일반) [Zhang, Lina; Lee, Yong-Min; Guo, Mian; Fukuzumi, Shunichi; Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Nam, Wonwoo] Univ Jinan, Sch Chem & Chem Engn, Jinan 250022, Peoples R China
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2020
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000175436
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/jacs.0c10159
- PubMed https://pubmed.ncbi.nlm.nih.gov/33186008
초록/요약
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.
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