Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity

Yen Hao Lin, Hanna Hinrika Cramer, Maurice Van Gastel, Yi Hsuan Tsai, Chi Yi Chu, Ting Shen Kuo, I. Ren Lee, Shengfa Ye, Eckhard Bill, Way Zen Lee

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2 Citations (Scopus)

Abstract

Metal-superoxo species are typically proposed as key intermediates in the catalytic cycle of dioxygen activation by metalloenzymes involving different transition metal cofactors. In this regard, while a series of Fe-, Co-, and Ni-superoxo complexes have been reported to date, well-defined Mn-superoxo complexes remain rather rare. Herein, we report two mononuclear MnIII-superoxo species, Mn(BDPP)(O2 •-) (2, H2BDPP = 2,6-bis((2-(S)-diphenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) and Mn(BDPBrP)(O2 •-) (2′, H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxyl-methyl-1-pyrrolidinyl)methyl)pyridine), synthesized by bubbling O2 into solutions of their MnII precursors, Mn(BDPP) (1) and Mn(BDPBrP) (1′), at -80 °C. A combined spectroscopic (resonance Raman and electron paramagnetic resonance (EPR) spectroscopy) and computational study evidence that both complexes contain a high-spin MnIII center (SMn = 2) antiferromagnetically coupled to a superoxo radical ligand (SOO• = 1/2), yielding an overall S = 3/2 ground state. Complexes 2 and 2′ were shown to be capable of abstracting a H atom from 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPO-H) to form MnIII-hydroperoxo species, Mn(BDPP)(OOH) (5) and Mn(BDPBrP)(OOH) (5′). Complexes 5 and 5′ can be independently prepared by the reactions of the isolated MnIII-aqua complexes, [Mn(BDPP)(H2O)]OTf (6) and [Mn(BDPBrP)(H2O)]OTf (6′), with H2O2 in the presence of NEt3. The parallel-mode EPR measurements established a high-spin S = 2 ground state for 5 and 5′.

Original languageEnglish
Pages (from-to)9756-9765
Number of pages10
JournalInorganic Chemistry
Volume58
Issue number15
DOIs
Publication statusPublished - 2019 Aug 5

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Lin, Y. H., Cramer, H. H., Van Gastel, M., Tsai, Y. H., Chu, C. Y., Kuo, T. S., Lee, I. R., Ye, S., Bill, E., & Lee, W. Z. (2019). Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity. Inorganic Chemistry, 58(15), 9756-9765. https://doi.org/10.1021/acs.inorgchem.9b00767