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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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Bill,  Eckhard
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Schnegg,  Alexander
Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Ye,  Shengfa
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(23), 10255-10260. doi:10.1021/jacs.0c02756.


Cite as: http://hdl.handle.net/21.11116/0000-0007-B460-1
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((BDPP)-P-Br)(OOH)](+) (1, (H2BDPP)-P-Br = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) was generated by treatment of a Mn-III-superoxo complex, Mn((BDPP)-P-Br)(O-2(center dot)) (2) with trifluoroacetic acid at -120 degrees 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((BDPP)-P-Br)(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((BDPP)-P-Br)(OOH) (3), also yields 1.