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


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'.

SUBMITTER: Lin YH 

PROVIDER: S-EPMC6685055 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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

Lin Yen-Hao YH   Cramer Hanna Hinrika HH   van Gastel Maurice M   Tsai Yi-Hsuan YH   Chu Chi-Yi CY   Kuo Ting-Shen TS   Lee I-Ren IR   Ye Shengfa S   Bill Eckhard E   Lee Way-Zen WZ  

Inorganic chemistry 20190722 15


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 Mn<sup>III</sup>-superoxo species, Mn(BDPP)(O<sub>2</sub><sup>•-</sup>) (<b>2</b>, H<sub>2</sub>BDPP = 2,6-bis((2-(<i>S</i>)-diphenylh  ...[more]

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