Bond cleavage is one of the most important transformations in radical cations. This process is much easier in radical ions than that in neutral species as a consequence of bond weakening resulting from the removal of an electron from a fully occupied orbital of the neutral substrate.1
In the present communication we report the results from our study on the generation and reactivity of sulfide radical cations. Photoinduced electron transfer by different sensitizers was employed for ionization of alkyl aryl sulfides; the effect of alkyl and the aryl substituents on the fragmentation rate constant was evaluated. Tools such as transient absorption spectroscopy and electrochemical methods were used in order to gain insight into the reaction mechanism, and to evaluate the different channels these radical cations would follow (Scheme 1).
