Fig. 1. Activation free energies for the XAT process and conformations of aminoalkyl radicals. Method: uwB97xd/def2svp-CPCM(MeCN). In brackets, energies obtained from second order perturbation theory in NBO analysis are shown (for radicals T3 and C1–C3, the sum of interactions for the two lone pairs is given). All energies are in kcal mol⁻¹.