Origins of Stabilization and Evidence for Charge Delocalization in the Bicyclo[3.2.1]octadienyl Anion and Related Species

Abstract

Bridged bicyclic allylic anions with ethene and allyl units in proximity possess enhanced stability over analogues lacking the ethene bridge. Experimental observations have encouraged much computational effort, and for many years claims for homoaromatic behaviour in anions were disputed. More recently, and especially with the advent of quantum mechanics methods that assess magnetic susceptibility, homoaromaticity has become accepted. This paper provides a review of work on this topic to date, and additional density functional theory calculations with the purpose of providing a general overview. The presence of homoaromaticity in anions of this class is supported, and their stability is augmented by inductive and counterion effects.