Finding a new pathway for acid-induced nitrite reduction reaction: formation of nitric oxide with hydrogen peroxide

Here, we report a new pathway for nitrite reduction chemistry, formation of cobalt-nitrosyl ({Co^II-NO}⁸) with H₂O₂ in the reaction of a Co^II-nitrito complex with a one-fold acid (H⁺) via the formation of a Co^II-nitrous acid intermediate ({Co^II-ONOH}). Mechanistic investigations using ¹⁵N-labeled-¹⁵NO₂^- revealed that the N-atom in the {Co^II-NO}⁸ complex is derived from the nitrito ligand, and H₂O₂ came from the homolysis of the ON-OH moiety. Spectral evidence supporting the formation of the Co^II-ONOH intermediate and the generation of H₂O₂ is also presented.