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

^*此作品的通信作者

化學系

研究成果: 雜誌貢獻 › 期刊論文 › 同行評審

82 引文斯高帕斯（Scopus）

摘要

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.

原文	英語
頁（從 - 到）	14186-14189
頁數	4
期刊	Journal of the American Chemical Society
卷	138
發行號	43
DOIs	https://doi.org/10.1021/jacs.6b08642
出版狀態	已發佈 - 2016 11月 2

ASJC Scopus subject areas

催化
一般化學
生物化學
膠體和表面化學

存取文件

10.1021/jacs.6b08642

其它文件與鏈接

CCDC 1521547: Experimental Crystal Structure Determination
Wang, C.-C. (Creator), Chang, H.-C. (Creator), Lai, Y.-C. (Creator), Fang, H. (Creator), Li, C.-C. (Creator), Hsu, H.-K. (Creator), Li, Z.-Y. (Creator), Lin, T.-S. (Creator), Kuo, T.-S. (Creator), Neese, F. (Creator), Ye, S. (Creator), Chiang, Y.-W. (Creator), Tsai, M.-L. (Creator), Liaw, W.-F. (Creator) & Lee, W.-Z. (Contributor), Unknown Publisher, 2016
DOI: 10.5517/ccdc.csd.cc1n2956, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1n2956&sid=DataCite
資料集: Dataset
CCDC 1521549: Experimental Crystal Structure Determination
Wang, C.-C. (Creator), Chang, H.-C. (Creator), Lai, Y.-C. (Creator), Fang, H. (Creator), Li, C.-C. (Creator), Hsu, H.-K. (Creator), Li, Z.-Y. (Creator), Lin, T.-S. (Creator), Kuo, T.-S. (Creator), Neese, F. (Creator), Ye, S. (Creator), Chiang, Y.-W. (Creator), Tsai, M.-L. (Creator), Liaw, W.-F. (Creator) & Lee, W.-Z. (Contributor), Unknown Publisher, 2016
DOI: 10.5517/ccdc.csd.cc1n2978, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1n2978&sid=DataCite
資料集: Dataset
CCDC 1521548: Experimental Crystal Structure Determination
Wang, C.-C. (Creator), Chang, H.-C. (Creator), Lai, Y.-C. (Creator), Fang, H. (Creator), Li, C.-C. (Creator), Hsu, H.-K. (Creator), Li, Z.-Y. (Creator), Lin, T.-S. (Creator), Kuo, T.-S. (Creator), Neese, F. (Creator), Ye, S. (Creator), Chiang, Y.-W. (Creator), Tsai, M.-L. (Creator), Liaw, W.-F. (Creator) & Lee, W.-Z. (Contributor), Unknown Publisher, 2016
DOI: 10.5517/ccdc.csd.cc1n2967, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1n2967&sid=DataCite
資料集: Dataset

引用此

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, 卷 138, 編號 43, 頁 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.",

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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

摘要

ASJC Scopus subject areas

存取文件

其它文件與鏈接

指紋

資料集

CCDC 1521547: Experimental Crystal Structure Determination

CCDC 1521549: Experimental Crystal Structure Determination

CCDC 1521548: Experimental Crystal Structure Determination

引用此