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 N,H20 including hydroxy-1,land 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 + H20, postulated to be a key step in the thermal DeNO, process for reducing NO to N2 in stationary power plants, (ii) deoxygenation of N-nitroso compounds and azoxy compounds, and (iii) nitrosation of amines.