Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer
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Lippard_Light-induced.pdf
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Author(s)
Jiang, Yunbo
Hayashi, Takahiro
Matsumura, Hirotoshi
Do, Loi H.
Majumdar, Amit
Lippard, Stephen J.
Moënne-Loccoz, Pierre
Date Issued
August 2014
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Jiang, Yunbo; Hayashi, Takahiro; Matsumura, Hirotoshi; Do, Loi H.; Majumdar, Amit; Lippard, Stephen J. and Moënne-Loccoz, Pierre. “ Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer.” Journal of the American Chemical Society 136, 36 (September 2014): 12524–12527 © 2014 American Chemical Society
Version
Final published version
Abstract
Two non-heme iron–nitrosyl species, [Fe₂(N-Et-HPTB)(O₂CPh)(NO)₂](BF4)₂(1a) and [Fe₂(N-Et-HPTB)(DMF)₂(NO)(OH)](BF₄)₃ (2a), are characterized by FTIR and resonance Raman spectroscopy. Binding of NO is reversible in both complexes, which are prone to NO photolysis under visible light illumination. Photoproduction of N₂O occurs in high yield for 1a but not 2a. Low-temperature FTIR photolysis experiments with 1a in acetonitrile do not reveal any intermediate species, but in THF at room temperature, a new {FeNO}⁷ species quickly forms under illumination and exhibits a ν(NO) vibration indicative of nitroxyl-like character. This metastable species reacts further under illumination to produce N₂O. A reaction mechanism is proposed, and implications for NO reduction in flavodiiron proteins are discussed.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja504343t
