Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)-Superoxo and Manganese(IV)-Peroxo Complexes.

Reactions of nonheme Fe(III) -superoxo and Mn(IV) -peroxo complexes bearing a common tetraamido macrocyclic ligand (TAML), namely [(TAML)Fe(III) (O2 )](2-) and [(TAML)Mn(IV) (O2 )](2-) , with nitric oxide (NO) afford the Fe(III) -NO3 complex [(TAML)Fe(III) (NO3 )](2-) and the Mn(V) -oxo complex [(TAML)Mn(V) (O)](-) plus NO2 (-) , respectively. Mechanistic studies, including density functional theory (DFT) calculations, reveal that M(III) -peroxynitrite (M=Fe and Mn) species, generated in the reactions of [(TAML)Fe(III) (O2 )](2-) and [(TAML)Mn(IV) (O2 )](2-) with NO, are converted into M(IV) (O) and (.) NO2 species through O-O bond homolysis of the peroxynitrite ligand. Then, a rebound of Fe(IV) (O) with (.) NO2 affords [(TAML)Fe(III) (NO3 )](2-) , whereas electron transfer from Mn(IV) (O) to (.) NO2 yields [(TAML)Mn(V) (O)](-) plus NO2 (-) .