TY - JOUR
T1 - Light-induced N2O production from a non-heme iron-nitrosyl dimer
AU - Jiang, Yunbo
AU - Hayashi, Takahiro
AU - Matsumura, Hirotoshi
AU - Do, Loi H.
AU - Majumdar, Amit
AU - Lippard, Stephen J.
AU - Moënne-Loccoz, Pierre
N1 - Publisher Copyright:
© 2014 American Chemical Society.
PY - 2014/9/10
Y1 - 2014/9/10
N2 - 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 η(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.
AB - 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 η(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.
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U2 - 10.1021/ja504343t
DO - 10.1021/ja504343t
M3 - Article
C2 - 25158917
AN - SCOPUS:84907485230
SN - 0002-7863
VL - 136
SP - 12524
EP - 12527
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 36
ER -