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 {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.
Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.
Nhut Giuc
NG
Tran
Harris
H
Kalyvas
Kelsey M
KM
Skodje
Takahiro
T
Hayashi
Pierre
P
Moënne-Loccoz
Paige E
PE
Callan
Jason
J
Shearer
Louis J
LJ
Kirschenbaum
Eunsuk
E
Kim
D005029:Ethylenediamines / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D009589:Nitrogen Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D019800:Phenol / Q000737:chemistry*
D005029:Ethylenediamines; D009589:Nitrogen Oxides; C005798:N,N,N',N'-tetramethylethylenediamine; D019800:Phenol; C073661:dinitrosyl iron complex; D007501:Iron; D009584:Nitrogen; D010100:Oxygen
Inorg Chem. 2006 Aug 21;45(17):6583-5
16903707
Nat Rev Drug Discov. 2007 Aug;6(8):662-80
17667957
Chem Res Toxicol. 2009 May;22(5):894-8
19374346
Nitric Oxide. 2009 Aug;21(1):1-13
19366636
Inorg Chem. 2004 Aug 9;43(16):5159-67
15285693
Chem Rev. 2002 Apr;102(4):993-1018
11942785
J Am Chem Soc. 2009 Jun 17;131(23):7964-5
19459625
J Biol Inorg Chem. 2009 Nov;14(8):1301-11
19662443
J Inorg Biochem. 2000 Nov;82(1-4):181-7
11132625
Proc Natl Acad Sci U S A. 2004 Mar 23;101(12):4003-8
15020765
J Am Chem Soc. 2004 Sep 8;126(35):10867-74
15339171
J Biol Chem. 1995 Dec 8;270(49):29244-9
7493954
Biofizika. 1965;10:167-8
14332030
J Am Chem Soc. 2008 Aug 20;130(33):10929-38
18661983
Inorg Chem. 2010 Sep 6;49(17):7644-6
20687531
Biochim Biophys Acta. 1968 Aug 13;160(3):311-20
4300590
Biochem Pharmacol. 2002 Feb 1;63(3):485-93
11853699
Proc Natl Acad Sci U S A. 1961 Sep 15;47:1374-84
13694929
J Proteome Res. 2009 Jul;8(7):3222-38
19415921
ACS Chem Biol. 2009 Mar 20;4(3):161-77
19267456
Methods Enzymol. 1996;269:41-55
8791636
J Biol Chem. 1990 Sep 5;265(25):15028-33
2168399
J Biol Chem. 2005 Dec 23;280(51):42172-80
16195232
Nature. 1964 Dec 19;204:1192
14264374
Inorg Chem. 2006 Jul 24;45(15):6041-7
16842012
Inorg Chem. 2005 Aug 8;44(16):5872-81
16060642
Chem Rev. 2002 Apr;102(4):1155-66
11942790
J Am Chem Soc. 2005 Apr 6;127(13):4550-1
15796501
Chem Rev. 2004 Feb;104(2):403-18
14871130
J Biol Inorg Chem. 2006 Apr;11(3):359-70
16520978
Inorg Chem. 2007 Jun 11;46(12):5110-7
17444639
Physiol Rev. 2007 Jan;87(1):315-424
17237348
Chem Rev. 2005 Jun;105(6):2457-70
15941219
Chemistry. 2010 Jul 19;16(27):8088-95
20533462
J Am Chem Soc. 2004 May 19;126(19):6005-16
15137765
Nature. 1965 Sep 18;207(5003):1246-9
4287143