The reaction of benzene with a ground state carbon atom, C(3Pj)

The reaction between benzene and a single ground state carbon atom, C(3Pj), which yields a C7H5 radical without a barrier in the exit channel, has been studied using density functional theory (B3LYP), Moller–Plesset perturbation theory, and the G2(B3LYP/MP2) and complete basis set (CBS) model chemistries. Comparing the computed reaction energies for the formation of various C7H5 radicals with experimental data suggests that the 1,2-didehydrocycloheptatrienyl radical (15) is observed in crossed-beams experiments at collision energies between 2 and 12 kcal mol−1. The carbon atom attacks the π-electron density of benzene and forms without entrance barrier a Cs symmetric complex (17T) in which the carbon atom is bound to the edge of benzene. From 17T, the insertion of the C atom into a benzene CC bond to yield triplet cycloheptatrienylidene (9T) is associated with a much lower barrier than the insertion into a CH bond to give triplet phenylcarbene (7T). As both steps are strongly exothermic, high energy vinyl...

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