The reaction mechanisms of radical formation by various bases were investigated through Density Functional Theory (DFT) calculations, using the Gaussian16 software package. If not stated otherwise, all calculations were performed in gas phase. The hybrid B3LYP functional and the augmented correlation-consistent polarized valence double-zeta (aug-cc-pVDZ) basis set were employed for H, C, N, and O, Li and Na, and K, using Basis Set Exchange -the (un)restricted formalism was adopted for open-shell and closed-shell species, respectively. Grimme's D3 damping function was used to account for dispersion corrections. Initial molecular structures of all reactants and products were generated with GaussView software, and each reactant and product were optimized individually. Subsequent calculations of the Hessian were performed to confirm the presence of true stationary minima on the potential energy surface (PES), with non-negative frequencies and converged forces. All the reported reaction energies (∆𝐺) are in kcal/mol and have been calculated using the sum of electronic and thermal free energies. To assess the validity of our choice of functional to describe the SET process, we also employed a range of functionals, finding a small deviation in the ∆𝐺 values. In particular, we used CAM-B3LYP, LC-wPBE and WB97XD, the latter two with and without dispersion (Table ).