Quasiclassical direct dynamics simulations are applied to a 4-fold degenerate rearrangement which yields a nonstatistical product distribution. The simulated product ratio agrees with experiment and is found to be entirely dynamically determined. Trajectory lifetimes are on the order of a low-frequency vibrational period. The interaction of reaction momentum with the geometric features of the potential surface produces selectivity despite a common energy barrier. A geometric model is described for qualitatively estimating much of the dynamically determined product ratio independently of trajectory calculations. The characteristics of this reaction are expected also to apply to others involving modestly stabilized diradical intermediates.

Isopropylamine diazeniumdiolate, IPA/NO, the product of the reaction of isopropylamine and nitric oxide, NO, decomposes in a pH dependent manner to afford nitroxyl, HNO, in the pH range of 13 to above 5 and NO below pH 7. Theoretical studies using B3LYP/6-311+G(d) density functional theory, the PCM and CPCM solvation models and the high accuracy CBS-QB3 method on the simplified model compound, methylamine diazeniumdiolate, predict a mechanism involving HNO production via decomposition of the unstable tautomer MeNN + (O − )NHO − . The production of NO at lower pH is predicted to result from fragmentation of the amide/NO adduct upon protonation of the amine nitrogen.