A Manganese(IV)-Hydroperoxo Intermediate Generated by Protonation of the Corresponding Manganese(III)-Superoxo Complex

Yen Hao Lin, Yury Kutin, Maurice Van Gastel, Eckhard Bill, Alexander Schnegg, Shengfa Ye, Way Zen Lee

    研究成果: 雜誌貢獻文章同行評審

    摘要

    Earlier work revealed that metal-superoxo species primarily function as radicals and/or electrophiles. Herein, we present ambiphilicity of a MnIII-superoxo complex revealed by its proton- A nd metal-coupled electron-transfer processes. Specifically, a MnIV-hydroperoxo intermediate, [Mn(BDPBrP)(OOH)]+ (1, H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) was generated by treatment of a MnIII-superoxo complex, Mn(BDPBrP)(O2â¢) (2) with trifluoroacetic acid at-120 °C. Detailed insights into the electronic structure of 1 are obtained using resonance Raman and multi-frequency electron paramagnetic resonance spectroscopies coupled with density functional theory calculations. Similarly, the reaction of 2 with scandium(III) triflate was shown to give a Mn(IV)/Sc(III) bridging peroxo species, [Mn(BDPBrP)(OO)Sc(OTf)n](3-n)+ (4). Furthermore, it is found that deprotonation of 1 quantitatively regenerates 2, and that one-electron oxidation of the corresponding MnIII-hydroperoxo species, Mn(BDPBrP)(OOH) (3), also yields 1.

    原文英語
    頁(從 - 到)10255-10260
    頁數6
    期刊Journal of the American Chemical Society
    142
    發行號23
    DOIs
    出版狀態已發佈 - 2020 六月 10

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)
    • Biochemistry
    • Colloid and Surface Chemistry

    指紋 深入研究「A Manganese(IV)-Hydroperoxo Intermediate Generated by Protonation of the Corresponding Manganese(III)-Superoxo Complex」主題。共同形成了獨特的指紋。

    引用此