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A Structurally Characterized Nonheme Cobalt–Hydroperoxo Complex Derived from Its Superoxo Intermediate via Hydrogen Atom Abstraction

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Fang,  Huayi
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

Lin,  Tien-Sung
Research Department Neese, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Ye,  Shengfa
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Wang, C.-C., Chang, H.-C., Lai, Y.-C., Fang, H., Li, C.-C., Hsu, H.-K., et al. (2016). A Structurally Characterized Nonheme Cobalt–Hydroperoxo Complex Derived from Its Superoxo Intermediate via Hydrogen Atom Abstraction. Journal of the American Chemical Society, 138(43), 14186-14189. doi:10.1021/jacs.6b08642.


Cite as: http://hdl.handle.net/21.11116/0000-0007-82DE-C
Abstract
Bubbling O2 into a THF solution of CoII(BDPP) (1) at −90 °C generates an O2 adduct, Co(BDPP)(O2) (3). The resonance Raman and EPR investigations reveal that 3 contains a low spin cobalt(III) ion bound to a superoxo ligand. Significantly, at −90 °C, 3 can react with 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPOH) to form a structurally characterized cobalt(III)-hydroperoxo complex, CoIII(BDPP)(OOH) (4) and TEMPO. Our findings show that cobalt(III)-superoxo species are capable of performing hydrogen atom abstraction processes. Such a stepwise O2-activating process helps to rationalize cobalt-catalyzed aerobic oxidations and sheds light on the possible mechanism of action for Co-bleomycin.