Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex

Chien Wei Chiang, Scott T. Kleespies, Heather D. Stout, Katlyn K. Meier, Po Yi Li, Emile L. Bominaar, Lawrence Que, Eckard Münck, Way Zen Lee

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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 languageEnglish
Pages (from-to)10846-10849
Number of pages4
JournalJournal of the American Chemical Society
Volume136
Issue number31
DOIs
Publication statusPublished - 2014 Aug 6

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Chiang, C. W., Kleespies, S. T., Stout, H. D., Meier, K. K., Li, P. Y., Bominaar, E. L., Que, L., Münck, E., & Lee, W. Z. (2014). Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex. Journal of the American Chemical Society, 136(31), 10846-10849. https://doi.org/10.1021/ja504410s