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

Lin, Yen-Hao; Kutin, Yuri; van Gastel, Maurice; Bill, Eckhard; Schnegg, Alexander; Ye, Shengfa; Lee, Way-Zen

doi:10.1021/jacs.0c02756

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

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van Gastel, Maurice
Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Ye, Shengfa
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences;
Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Lin, Y.-H., Kutin, Y., van Gastel, M., Bill, E., Schnegg, A., Ye, S., et al. (2020). A Manganese(IV)-Hydroperoxo Intermediate Generated by Protonation of the Corresponding Manganese(III)-Superoxo Complex. Journal of the American Chemical Society, 142(33), 10255-10260. doi:10.1021/jacs.0c02756.

Cite as: https://hdl.handle.net/21.11116/0000-0006-B44D-9

Abstract

Earlier work revealed that metal-superoxo species primarily function as radicals and/or electrophiles. Herein, we present ambiphilicity of a Mn^III-superoxo complex revealed by its proton- and metal-coupled electron-transfer processes. Specifically, a Mn^IV-hydroperoxo intermediate, [Mn(BDP^BrP)(OOH)]⁺ (1, H₂BDP^BrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) was generated by treatment of a Mn^III-superoxo complex, Mn(BDP^BrP)(O₂^•) (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(BDP^BrP)(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 Mn^III-hydroperoxo species, Mn(BDP^BrP)(OOH) (3), also yields 1.