Abstract
O2 bubbling into a THF solution of FeII(BDPP) (1) at -80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and Mössbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm-1, which can be assigned to the ν(O-O) of a bound superoxide, while the latter reveals the presence of a high-spin iron(III) center that is exchange-coupled to the superoxo ligand, like the FeIII-O 2- pair found for the O2 adduct of 4-nitrocatechol-bound homoprotocatechuate 2,3-dioxygenase. Lastly, 2 oxidizes dihydroanthracene to anthracene, supporting the notion that Fe III-O2- species can carry out H atom abstraction from a C-H bond to initiate the 4-electron oxidation of substrates proposed for some nonheme iron enzymes.
Original language | English |
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Pages (from-to) | 10846-10849 |
Number of pages | 4 |
Journal | Journal of the American Chemical Society |
Volume | 136 |
Issue number | 31 |
DOIs | |
Publication status | Published - 2014 Aug 6 |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry
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CCDC 1020020: Experimental Crystal Structure Determination
Chiang, C. (Creator), Kleespies, S. T. (Creator), Stout, H. D. (Creator), Meier, K. K. (Creator), Li, P. (Creator), Bominaar, E. L. (Creator), Que, L. (Contributor), Münck, E. (Contributor) & Lee, W. (Creator), Unknown Publisher, 2014
DOI: 10.5517/cc137dwm, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc137dwm&sid=DataCite
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