Nitric Oxide Oxygenation Reactions of Cobalt-Peroxo and Cobalt-Nitrosyl Complexes

Here, we report a comparative study of nitric oxide oxidation (NOO) reactions of Co^III-peroxo (Co^III-O₂^2-) and Co-nitrosyl ({CoNO}⁸) complexes bearing the same N₄-donor ligand (HMTETA) framework. In this regard, we prepared and characterized two new [(HMTETA)Co^III(O₂^2-)]⁺ (2, S = 2) and [(HMTETA)Co(NO)]²⁺ (3, S = 1) complexes from [(HMTETA)Co^II(CH₃CN)₂]²⁺ (1). Both complexes (2 and 3) are characterized by different spectroscopic measurements, including their DFT-optimized structures. Complex 2 produces Co^II-nitrato [(HMTETA)Co^II(NO₃^-)]⁺ (Co^II-NO₃^-, 4) complex in the presence of NO. In contrast, when 3 reacted with a superoxide (O₂^•-) anion, it generated Co^II-nitrito [(HMTETA)Co^II(NO₂^-)]⁺ (Co^II-NO₂^-, 5) with O₂ evolution. Experiments performed using ^18/16O-labeled superoxide (¹⁸O₂^•-/¹⁶O₂^•-) showed that O₂ originated from the O₂^•- anion. Both the NOO reactions are believed to proceed via a presumed peroxynitrite (PN) intermediate. Although we did not get direct spectral evidence for the proposed PN species, the mechanistic investigation using 2,4-di-tert-butylphenol indirectly suggests the formation of a PN intermediate. Furthermore, tracking the source of the N-atom in the above NOO reactions using ¹⁵N-labeled nitrogen (¹⁵NO) revealed N-atoms in 4 (Co^II-¹⁵NO₃^-) and 5 (Co^II-¹⁵NO₂^-) derived from the ¹⁵NO moiety.