Energetics and Mechanisms for Reactions Involving Nitrosamide, Hydroxydiazenes, and Diimide N-Oxides

Using ab initio techniques, we have solved for the geometries and energies of nine isomers of N₂H₂O including hydroxy-1,1- and hydroxy-1,2-diazenes¹ (e.g., HNNOH), nitrosamide (H₂N—NO), and diimide N-oxides (HNN(→O)H). The heats of formation obtained from these calculations are used to examine several chemical processes including (i) the reaction H₂N + NO→N₂ + H₂O, postulated to be a key step in the thermal DeNO_x process for reducing NO to N₂ in stationary power plants, (ii) deoxygenation of N-nitroso compounds and azoxy compounds, and (iii) nitrosation of amines.