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

Research output: Contribution to journalArticle

56 Citations (Scopus)

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

Fingerprint

3,4-dihydroxyphenylacetate 2,3-dioxygenase
Iron
Raman Spectrum Analysis
Anthracene
Vibration
Superoxides
Vibrations (mechanical)
Enzymes
Ligands
Spectroscopy
Electrons
Atoms
Oxidation
Substrates
4-nitrocatechol
anthracene

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., ... 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

Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex. / Chiang, Chien Wei; Kleespies, Scott T.; Stout, Heather D.; Meier, Katlyn K.; Li, Po Yi; Bominaar, Emile L.; Que, Lawrence; Münck, Eckard; Lee, Way Zen.

In: Journal of the American Chemical Society, Vol. 136, No. 31, 06.08.2014, p. 10846-10849.

Research output: Contribution to journalArticle

Chiang, CW, Kleespies, ST, Stout, HD, Meier, KK, Li, PY, Bominaar, EL, Que, L, Münck, E & Lee, WZ 2014, 'Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex', Journal of the American Chemical Society, vol. 136, no. 31, pp. 10846-10849. https://doi.org/10.1021/ja504410s
Chiang CW, Kleespies ST, Stout HD, Meier KK, Li PY, Bominaar EL et al. Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex. Journal of the American Chemical Society. 2014 Aug 6;136(31):10846-10849. https://doi.org/10.1021/ja504410s
Chiang, Chien Wei ; Kleespies, Scott T. ; Stout, Heather D. ; Meier, Katlyn K. ; Li, Po Yi ; Bominaar, Emile L. ; Que, Lawrence ; Münck, Eckard ; Lee, Way Zen. / Characterization of a paramagnetic mononuclear nonheme iron-superoxo complex. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 31. pp. 10846-10849.
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