12 Reaction mechanisms : Part (i) Radical and radical ion reactions

Abstract

This chapter provides an overview of the 2003 literature pertaining to the mechanism and kinetics of reactions involving neutral free radicals and radical ions in solution. This overview begins by highlighting significant contributions to our understanding of fundamental classes of reactions: atom abstraction, addition, and fragmentation. Afterwards, rearrangement reactions, which are generally intramolecular variants of these fundamental classes, are examined. Quite noteworthy is the fact that a significant number of papers in 2003 involved the use of computational chemistry, density functional theory (B3LYP) in particular, to examine mechanisms of free radical and radical ion reactions. The ability of these methods to reproduce experimental data is impressive, giving workers in this area the confidence to make some intriguing predictions. A few examples of the use of radical reactions in synthesis are interspersed throughout this report. However, the coverage of this important area is very much limited to truly unusual transformations (from a mechanistic perspective).