Theoretical study of molecular nitrogen oxidation with vanadium peroxo complexes

The structure and reactivity toward molecular nitrogen of vanadium diperoxo complexes, as well as influence of protonation and coordination of trifluoroacetate on reactivity, were studied using the density functional method. It was ascertained that ozonide [V(O3)O2]- is the most stable form of the initial complex. The triplet state of the complex is formed with small energy expenses for electron transfer from the peroxo ligand to vanadium atom to form VIV. Transfer of O atom to N2 molecule to form N2O is possible for several transition states. The nature of possible complexes and transition states retains upon protonation, but the number of different structures increases depending on the ligand and the site of proton addition