Computational study on the 1,2-rearrangement in β-(nitroxy)vinyl and β-(acetoxy)vinyl radicals

Abstract

The 1,2-nitroxyl and 1,2-acetoxyl rearrangement in β-(nitroxy)vinyl and β-(acetoxy)vinyl radicals 13a and 13b, respectively, has been studied for the gas phase with various ab initio and density functional methods. The energetically most favorable pathway for 13a is calculated to proceed via reversible fragmentation/radical addition through transition state I-19a. In the case of 13b, rearrangement through a five-membered ring transition state III-16b and the fragmentation/radical addition pathway via transition state I-19b are competing processes. Mulliken and natural population analysis reveal a certain degree of charge separation in III-16a/b that may indicate a potential solvent effect on..