Phenol nitration induced by an {Fe(NO)2}10 dinitrosyl iron complex

Nhut Giuc Tran, Harris Kalyvas, Kelsey M. Skodje, Takahiro Hayashi, Pierre Moenne-Loccoz, Paige E. Callan, Jason Shearer, Louis J. Kirschenbaum, Eunsuk Kim

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

Cellular dinitrosyl iron complexes (DNICs) have long been considered NO carriers. Although other physiological roles of DNICs have been postulated, their chemical functionality outside of NO transfer has not been demonstrated thus far. Here we report the unprecedented dioxygen reactivity of a N-bound {Fe(NO)2}10 DNIC, [Fe(TMEDA)(NO)2] (1). In the presence of O2, 1 becomes a nitrating agent that converts 2,4,-di-tert-butylphenol to 2,4-di-tert-butyl-6-nitrophenol via formation of a putative iron-peroxynitrite [Fe(TMEDA)(NO)(ONOO)] (2) that is stable below -80 ̊C. Iron K-edge X-ray absorption spectroscopy on 2 supports a five-coordinated metal center with a bound peroxynitrite in a cyclic bidentate fashion. The peroxynitrite ligand of 2 readily decays at increased temperature or under illumination. These results suggest that DNICs could have multiple physiological or deleterious roles, including that of cellular nitrating agents.

Original languageEnglish (US)
Pages (from-to)1184-1187
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number5
DOIs
StatePublished - Feb 9 2011

Fingerprint

Nitration
Phenol
Phenols
Peroxynitrous Acid
Iron
2,4-di-tert-butylphenol
X-Ray Absorption Spectroscopy
Nitrophenols
X ray absorption spectroscopy
Lighting
Metals
Oxygen
Ligands
Temperature
dinitrosyl iron complex
phenyllithium

ASJC Scopus subject areas

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

Cite this

Tran, N. G., Kalyvas, H., Skodje, K. M., Hayashi, T., Moenne-Loccoz, P., Callan, P. E., ... Kim, E. (2011). Phenol nitration induced by an {Fe(NO)2}10 dinitrosyl iron complex. Journal of the American Chemical Society, 133(5), 1184-1187. https://doi.org/10.1021/ja108313u

Phenol nitration induced by an {Fe(NO)2}10 dinitrosyl iron complex. / Tran, Nhut Giuc; Kalyvas, Harris; Skodje, Kelsey M.; Hayashi, Takahiro; Moenne-Loccoz, Pierre; Callan, Paige E.; Shearer, Jason; Kirschenbaum, Louis J.; Kim, Eunsuk.

In: Journal of the American Chemical Society, Vol. 133, No. 5, 09.02.2011, p. 1184-1187.

Research output: Contribution to journalArticle

Tran, NG, Kalyvas, H, Skodje, KM, Hayashi, T, Moenne-Loccoz, P, Callan, PE, Shearer, J, Kirschenbaum, LJ & Kim, E 2011, 'Phenol nitration induced by an {Fe(NO)2}10 dinitrosyl iron complex', Journal of the American Chemical Society, vol. 133, no. 5, pp. 1184-1187. https://doi.org/10.1021/ja108313u
Tran, Nhut Giuc ; Kalyvas, Harris ; Skodje, Kelsey M. ; Hayashi, Takahiro ; Moenne-Loccoz, Pierre ; Callan, Paige E. ; Shearer, Jason ; Kirschenbaum, Louis J. ; Kim, Eunsuk. / Phenol nitration induced by an {Fe(NO)2}10 dinitrosyl iron complex. In: Journal of the American Chemical Society. 2011 ; Vol. 133, No. 5. pp. 1184-1187.
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