Dynamics of the degenerate rearrangement of bicyclo[3.1.0]hex-2-ene

Abstract

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.