A first reasonable guess would then be the reduction of nitrobenzene via a single electron transfer (SET) from the anionic organic base. Such SET can happen following either an outer-or inner-sphere mechanism, that is, with the formation of [1X] + cation adduct first and then the reduction from a dissociated salt (nonbonded), or the concomitant involvement of all species (bonded). The former process is predicted to be highly endothermic and is therefore discarded (Scheme S1-S5, Table ). The latter is predicted to be exothermic for the t BuLi and LDA, whereas slightly endothermic for the remaining anionic organic bases, which is further decreased if a fully dissociated base is considered (Figure , Scheme S6-S11, Table ). To assess these computational results, we performed comparative spin quantification experiments for [1] mixed with a solution of KHMDS and L 1 in THF (Figure ). We choose this combination as it provided clear spectra where possible artefacts from the nuclear spin were not a concern (Figure ). By keeping an equimolar ratio between [1] and KHMDS, while increasing that of L 1 from 1:0.1 to 1:1, we observe a clear increase in the number of radicals (Figure ), confirming that a fully dissociated alkali salt undergoes a more favourable SET. Still, this is predicted to be endothermic with a transition state very close to the products ((1.1) & (1.2) in Figure ) -the transition state is approximated by scanning the broken symmetry electronic state with explicit THF molecules coordinating the cation (Scheme S6 bottom ), otherwise the reaction coordinate is not well-defined. This calculated potential energy surface would render the process highly skewed towards the reactants and therefore EPR silent, in contrast to what has been measured. Thus, we explore other options that would make the process thermodynamically viable.