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Title: Phenol Nitration Induced by an {Fe(NO)2}10 Dinitrosyl Iron Complex

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 {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.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE SC OFFICE OF SCIENCE (SC)
OSTI Identifier:
1041907
Report Number(s):
BNL-97585-2012-JA
Journal ID: ISSN 0002-7863; JACSAT; TRN: US201212%%318
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 133; Journal Issue: 5; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ILLUMINANCE; IRON; IRON COMPLEXES; NITRATION; PHENOL

Citation Formats

Tran, N, Kalyvas, H, Skodje, K, Hayashi, T, Moenne-Loccoz, P, Callan, P, Shearer, J, Kirschenbaum, L, and Kim, E. Phenol Nitration Induced by an {Fe(NO)2}10 Dinitrosyl Iron Complex. United States: N. p., 2011. Web. doi:10.1021/ja108313u.
Tran, N, Kalyvas, H, Skodje, K, Hayashi, T, Moenne-Loccoz, P, Callan, P, Shearer, J, Kirschenbaum, L, & Kim, E. Phenol Nitration Induced by an {Fe(NO)2}10 Dinitrosyl Iron Complex. United States. https://doi.org/10.1021/ja108313u
Tran, N, Kalyvas, H, Skodje, K, Hayashi, T, Moenne-Loccoz, P, Callan, P, Shearer, J, Kirschenbaum, L, and Kim, E. Sat . "Phenol Nitration Induced by an {Fe(NO)2}10 Dinitrosyl Iron Complex". United States. https://doi.org/10.1021/ja108313u.
@article{osti_1041907,
title = {Phenol Nitration Induced by an {Fe(NO)2}10 Dinitrosyl Iron Complex},
author = {Tran, N and Kalyvas, H and Skodje, K and Hayashi, T and Moenne-Loccoz, P and Callan, P and Shearer, J and Kirschenbaum, L and Kim, E},
abstractNote = {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.},
doi = {10.1021/ja108313u},
url = {https://www.osti.gov/biblio/1041907}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 5,
volume = 133,
place = {United States},
year = {2011},
month = {12}
}