Phenol Nitration Induced by an {Fe(NO)2}10 Dinitrosyl Iron Complex
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 {l_brace}Fe(NO){sub 2}{r_brace}{sup 10} DNIC, [Fe(TMEDA)(NO){sub 2}] (1). In the presence of O{sub 2}, 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.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE SC OFFICE OF SCIENCE (SC)
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 1041907
- Report Number(s):
- BNL-97585-2012-JA; JACSAT; TRN: US201212%%318
- Journal Information:
- Journal of the American Chemical Society, Vol. 133, Issue 5; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
Similar Records
Unusual Synthetic Pathway for an {Fe(NO)2}9 Dinitrosyl Iron Complex (DNIC) and Insight into DNIC Electronic Structure via Nuclear Resonance Vibrational Spectroscopy
Study of the steam distillation of phenolic compounds using ultraviolet spectrometry