Abstract
Isomerization is an important reaction mode of organic transformations. Although extensive works have been carried out for isomerization reactions of carbocations and free radicals, few studies have been reported on isomerization reactions of radical cations. In the present work, we would like to report full computational studies of structures and reactivity of peroxy radical cations, which are formed by reactions of molecular oxygen with various aliphatic and aromatic alkenes, and the corresponding carbonyl oxide radical cations that may be formed by a hydrogen, a methyl, or a phenyl migration in the peroxy radical cations.
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