Structure and Reactivity of Radical Ions: New Twists on Old Concepts

Abstract

Electron transfer is the simplest reaction possible, yet it has a profound impact on the structure and reactivity of organic compounds. These changes allow a new look at some of the fundamental concepts that are used to explain organic chemistry, such as symmetry, aromaticity, and bonding. The results from high‐level electronic structure calculations are used to analyze the mechanistic differences in the pericyclic reactions of simple hydrocarbons and their radical cation counterparts. The importance of state symmetry correlation, Jahn–Teller distortions, delocalization, and fractional bonding for the reaction pathways of hydrocarbon radical cations is discussed.