Remarkable Acid Catalysis in Proton-Coupled Electron-Transfer Reactions of a Chromium(III)-Superoxo Complex
- 등재 SCIE, SCOPUS
- 발행기관 American Chemical Society
- 발행년도 2018
- URI http://www.dcollection.net/handler/ewha/000000151954
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/jacs.8b02303
- 저작권 이화여자대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
Much enhanced acid catalysis was observed in oxygen atom transfer (OAT) reactions by a mononuclear nonheme Cr(III)-superoxo complex, [(Cl)(TMC)CrIII(O2)]+ (1), in the presence of triflic acid. In the acid-catalyzed reactions, the reactivity of 1 in OAT of thioanisole was enhanced significantly, showing more than 104-fold acceleration in rate. Electron transfer (ET) from electron donors to 1 also occurred only in the presence of HOTf. The enhanced reactivity of 1 by HOTf was explained by proton-coupled electron transfer from electron donors, such as ferrocene, to 1 in light of the Marcus theory of ET. The present study reports for the first time the dramatic proton effect on the chemical properties of metal-superoxo species. © 2018 American Chemical Society.
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