Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 133, Issue 5, Pages 1184-1187Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja108313u
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Funding
- Brown University
- Camille and Henry Dreyfus New Faculty Award Program
- NIH [GM74785, P20 RR-016464]
- NSF [CH-0844623]
- Vertex pharmaceutical scholarship
- DOE [98CH1086]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0844234] Funding Source: National Science Foundation
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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 degrees 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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