Correlation of calculated halonium ion structures with product distributions from fluorine substituted terminal alkenes

Calculated equilibrium geometries, bond lengths, and charge densities were performed on halonium ions derived by the addition of halogen electrophiles to fluoro-substituted terminal alkenes. The calculated structures correlate with regiochemical product distributions from ring-opening of halonium ions by anions or by the solvent methanol. Calculated halonium ion structures and the Hammond postulate are utilized to predict the regiochemical product distributions for reactions of halogens with fluoroalkenes that are not investigated experimentally.