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. 2011 Feb 9;133(5):1184-7.
doi: 10.1021/ja108313u. Epub 2011 Jan 18.

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

Nhut Giuc Tran  1 , Harris Kalyvas, Kelsey M Skodje, Takahiro Hayashi, Pierre Moënne-Loccoz, Paige E Callan, Jason Shearer, Louis J Kirschenbaum, Eunsuk Kim
Affiliations

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

Nhut Giuc Tran et al. J Am Chem Soc. .

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 O(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.

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Figures

Figure 1
Figure 1
UV-Vis (A) and IR (B) spectra of [Fe(TMEDA)(NO)2] (1) (black dashed line), and of the putative intermediate [Fe(TMEDA)(NO)(ONOO)] (2) (red) at −80 °C in dichloromethane.
Figure 2
Figure 2
A) XANES region of the XAS for 1 (green), 2 (red) and the thermal decomposition product (black). B) Experimental (red solid line) and simulated (blue dashed line) magnitude FT k3 EXAFS data for 2. Best fit includes: shell #1: 2 N scatterers, r = 2.14(1) Å, σ2 = 0.003(2) Å2; O2NO shell: 1 O2NO scatterer, r1 = 1.91(1) Å, r2 = 1.91 Å (restrained), σ2 = 0.002(1) Å2, φ = 98(7)°; NO shell: 1 NO scatterer, r = 1.67(1) Å; σ2 = 0.008(2) Å2; θ = 192(2)°. Eo = 7120.4 eV. ε2 = 0.57.
Figure 3
Figure 3
IR spectra of a [Fe(TMEDA)(NO)(ONOO)] (2) in CH2Cl2 at 11 K before (black) and after illumination (red). The dark minus illuminated difference spectrum is also shown (blue). Sharp IR bands are from dichloromethane.
Scheme 1
Scheme 1
Chart 1
Chart 1
Dinitrosyl iron complexes (DNICs)
See this image and copyright information in PMC

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