The Rearrangement Reaction of CH₃SNO₂to CH₃SONO Studied by a Density Functional Theory Method

Abstract

Several critical geometries associated with the rearrangement of CH 3 SNO 2 to CH 3 SONO are calculated with the density functional theory (DFT) method and compared with those of the ab initio molecular orbital methods. There are two probable pathways for this rearrangement, one involving the transition state of an oxygen migration and the other through the homolytic decomposition to radicals. The reaction barrier via the transition state is about 60 kcal/mol and the decomposition energy into radicals about 35 kcal/mol, suggesting that the reaction pathway via the homolytic cleavage to radical species is energetically favorable. Since even the homolytic cleavage requires large energies, the rearrangement reaction is unlikely without the aid of catalysts.