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

Chun Chieh Wang, Hao Ching Chang, Yei Chen Lai, Huayi Fang, Chieh Chin Li, Hung Kai Hsu, Zong Yan Li, Tien Sung Lin, Ting Shen Kuo, Frank Neese, Shengfa Ye, Yun Wei Chiang, Ming Li Tsai, Wen Feng Liaw, Way Zen Lee

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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.

Original languageEnglish
Pages (from-to)14186-14189
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number43
DOIs
Publication statusPublished - 2016 Nov 2

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Wang, C. C., Chang, H. C., Lai, Y. C., Fang, H., Li, C. C., Hsu, H. K., Li, Z. Y., Lin, T. S., Kuo, T. S., Neese, F., Ye, S., Chiang, Y. W., Tsai, M. L., Liaw, W. F., & Lee, W. Z. (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. https://doi.org/10.1021/jacs.6b08642