Abstract
In this paper the results from time-resolved experiments (pulse radiolysis, laser photolysis) on the formation of radical cations derived from styrene type olefins in solvents of different polarity are presented. The free olefin radical cations formed by charge transfer (in cyclohexane), two photon ionization or one electron oxidation (in aqueous solutions) dimerize to distonic radical cations or react with nucleophiles to produce benzyl type radicals. The decay of the dimer cation ArC .HCH 2CH 2C +HAr seems to be determined by their ionic state: cationic polymerization in the case of free radical cations (one electron transfer ionization of styrenes), and intramolecular rearrangement to molecular dimer structures in the presence of counter ions [triplet sensitized electron transfer as reported by Schepp and Johnston (1994) J. Am. Chem. Soc. 116, 6895].
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