Properties and Reactivity of Gaseous Distonic Radical Ions with Aryl Radical Sites

Many different experimental techniques now exist for generating aryl distonic ions and examining their structures and chemical properties in mass spectrometers. Numerous research groups are involved in this research, with interests ranging from fundamental properties of neutral and charged mono- and polyradicals to exploration of radical-induced dissociation of biopolymers. The properties and reactivity of a variety of small cations with aryl radical sites have been thoroughly examined both theoretically and experimentally. These distonic ions have been found to be stable molecules with very different properties from those of the isomeric conventional radical cations. Much of their reactivity closely resembles that of related neutral radicals as hydrogen-atom abstraction and addition reactions are common. However, when the charge can delocalize into the benzene ring containing the radical site, also nucleophilic addition reactions to the radical site have been observed.