| Autor: |
Chiang CW; Department of Chemistry, National Taiwan Normal University , Taipei 11677, Taiwan (ROC)., Kleespies ST, Stout HD, Meier KK, Li PY, Bominaar EL, Que L Jr, Münck E, Lee WZ |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Chemical Society [J Am Chem Soc] 2014 Aug 06; Vol. 136 (31), pp. 10846-9. Date of Electronic Publication: 2014 Jul 24. |
| DOI: |
10.1021/ja504410s |
| Abstrakt: |
O2 bubbling into a THF solution of Fe(II)(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 Fe(III)-O2(-) 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. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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