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-NO}) with HO in the reaction of a Co-nitrito complex with a one-fold acid (H) via the formation of a Co-nitrous acid intermediate ({Co-ONOH}). Mechanistic investigations using N-labeled-NO revealed that the N-atom in the {Co-NO} complex is derived from the nitrito ligand, and HO came from the homolysis of the ON-OH moiety. Spectral evidence supporting the formation of the Co-ONOH intermediate and the generation of HO is also presented.