Fig. 6. DFT-computed pathways for the generation of the N-centered radical and 1,5-HAT process.

1a is reducted by EY²⁻(T1)* to give 1a⁻, followed the leaving of ${\mathrm{CF}}_3{\mathrm{C}}_6{\mathrm{H}}_4{\mathrm{CO}}_2^{-}$ group, which is thermodynamically favorable. The N_radical overcomes a relatively low barrier (7.7 kcal ⋅ mol⁻¹) to give C_radical. The Gaussian 09 level of M06-2X/6-311++G(d,p)-SMD(DMAc)//B3LYP/6-31+G(d) was used.