CIDNP evidence for a ‘hot’ carbocation formed by electron transfer between two radicals

Abstract

The radical pair (2), containing 2-phenylethyl and m-chlorobenzoyloxy radicals, produced from β-phenyl[α,α-²H₂]propionyl m-chlorobenzoyl peroxide (1), gives rearranged products; the observations of CIDNP and product analyses suggest that the 2-phenylethyl carbocation initially produced by electron transfer within the radical pair is a ‘hot’ carbocation which retains the ground state configuration of its neutral radical precursor.