Fragmentation reactions of radical cations

This paper summarizes most of the recent work by our group on the kinetic aspects of a variety of fragmentation reactions of radical cations involving the cleavage of C-H, O-H, C-C, and C-S bonds. In particular, the problems that have been addressed concern: (a) the carbon acidity/oxygen acidity dichotomy in the fragmentation of aryl- and thioarylalkanol radical cations; (b) the decarboxylation of aryl and thioarylacetic acid radical cations; (c) the structural factors influencing the rate of C-S bond cleavage in the radical cations of phenyl alkyl sulfides. The results presented and discussed have allowed us to recognize the important role played by the electron reorganization energy, associated with the intramolecular electron transfer from the scissile bond to the SOMO, with respect to the dynamics and mechanism of the fragmentation process in the radical cation. Copyright (c) 2006 John Wiley & Sons, Ltd.