Dynamics of anilinium radical alpha-heterolytic fragmentation processes. Electrofugal group, substituent, and medium effects on disilylation, decarboxylation, and retro-aldol cleavage pathways

Ion radicals are intermediates in several ground-state and excited-state redox reactions. A single electron transfer (SET) process has been used to look at the relevance of ion radical reaction dynamics. It is concluded that Beta-hydroxyanilinium radicals are less reactive than their analogues, and observations demonstrated that cation radicals derived from tertiary diamines occur as through-space three-electron N-N bonded structures.