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

doi:10.1021/jacs.6b08642

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

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

57 Citations (Scopus)

Abstract

Bubbling O₂ into a THF solution of Co^II(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, Co^III(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 language	English
Pages (from-to)	14186-14189
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	43
DOIs	https://doi.org/10.1021/jacs.6b08642
Publication status	Published - 2016 Nov 2

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.6b08642

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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

Wang, CC, Chang, HC, Lai, YC, Fang, H, Li, CC, Hsu, HK, Li, ZY, Lin, TS, Kuo, TS, Neese, F, Ye, S, Chiang, YW, Tsai, ML, Liaw, WF & Lee, WZ 2016, 'A Structurally Characterized Nonheme Cobalt-Hydroperoxo Complex Derived from Its Superoxo Intermediate via Hydrogen Atom Abstraction', Journal of the American Chemical Society, vol. 138, no. 43, pp. 14186-14189. https://doi.org/10.1021/jacs.6b08642

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

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.",

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

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AU - Wang, Chun Chieh

AU - Chang, Hao Ching

AU - Lai, Yei Chen

AU - Fang, Huayi

AU - Li, Chieh Chin

AU - Hsu, Hung Kai

AU - Li, Zong Yan

AU - Lin, Tien Sung

AU - Kuo, Ting Shen

AU - Neese, Frank

AU - Ye, Shengfa

AU - Chiang, Yun Wei

AU - Tsai, Ming Li

AU - Liaw, Wen Feng

AU - Lee, Way Zen

PY - 2016/11/2

Y1 - 2016/11/2

N2 - 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.

AB - 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.

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

Abstract

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CCDC 1521549: Experimental Crystal Structure Determination

CCDC 1521547: Experimental Crystal Structure Determination

CCDC 1521548: Experimental Crystal Structure Determination

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

Abstract

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CCDC 1521549: Experimental Crystal Structure Determination

CCDC 1521547: Experimental Crystal Structure Determination

CCDC 1521548: Experimental Crystal Structure Determination

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