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 language | English |
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Pages (from-to) | 14186-14189 |
Number of pages | 4 |
Journal | Journal of the American Chemical Society |
Volume | 138 |
Issue number | 43 |
DOIs | |
Publication status | Published - 2016 Nov 2 |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry
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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
Dataset
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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
Dataset
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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
Dataset