Formation of carbonium ions, carbanions and carbanion-pairs in irradiated solutions, and the reactivity of these intermediates

Abstract

Pulse radiolysis studies of a variety of compounds containing the phenyl group, in solution in 1,2-dichloroethane, have led to the observation of the arylcarbenium ions, PhCH⁺₂, Ph₂CH⁺ and Ph₃C⁺. Rate constants for electrophilic reactions of these carbocations with a variety of nucleophiles have been determined. The trends in the rate constants reflect the steric and electronic effects. The observed reactivities provide some guidance regarding the role of these intermediates in radiation chemical systems and in organic mechanisms more generally.