Light-Induced N₂O Production from a Non-Heme Iron–Nitrosyl Dimer

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.