Abstract
The factors which control the reactivity of alkyl free radicals R˙ in reaction (i) are studied. The reactivity [graphic omitted] R′→ R – OH + R′CO˙2(i), of R˙ in (i) depends on the key orbital interaction between the SOMO of the radical and the LUMO of the peroxyacid. This interaction involves two contributions: (i) the energy gap SOMO–LUMO and (ii) the overlap SOMO–LUMO. In reaction (i) the main factor is overlap control which depends on spin delocalisation in the radical R˙. This proves that reaction (i) does not involve electron transfer. The energy gap control, which depends on the nucleophilic character of R˙, is only observed when the first factor is constant along a series of R˙.
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