TY - JOUR
T1 - Phenol nitration induced by an {Fe(NO)2}10 dinitrosyl iron complex
AU - Tran, Nhut Giuc
AU - Kalyvas, Harris
AU - Skodje, Kelsey M.
AU - Hayashi, Takahiro
AU - Moënne-Loccoz, Pierre
AU - Callan, Paige E.
AU - Shearer, Jason
AU - Kirschenbaum, Louis J.
AU - Kim, Eunsuk
PY - 2011/2/9
Y1 - 2011/2/9
N2 - 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.
AB - 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.
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U2 - 10.1021/ja108313u
DO - 10.1021/ja108313u
M3 - Article
C2 - 21244001
AN - SCOPUS:79551701746
SN - 0002-7863
VL - 133
SP - 1184
EP - 1187
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 5
ER -