Mechanistic studies of NOx reduction reactions involving copper complexes: encouragement of DFT calculations.

The reduction of nitrogen oxides (NOx), which is mainly mediated by metalloenzymes and metal complexes, is a critical process in the nitrogen cycle and environmental remediation. This Frontier article highlights the importance of density functional theory (DFT) calculations to gain mechanistic insights into nitrite (NO2-) and nitric oxide (NO) reduction reactions facilitated by copper complexes by focusing on two key processes: the reduction of NO2- to NO by a monocopper complex, with special emphasis on the concerted proton-electron transfer, and the reduction of NO to N2O by a dicopper complex, which involves N-N bond formation, N2O2 isomerization, and N-O bond cleavage. These findings underscore the utility of DFT calculations in unraveling complicated reaction mechanisms and offer a foundation for future research aimed at improving the reactivity of transition metal complexes in NOx reduction reactions.