There are several works in the literature reporting on the reducing capacity of tert-butoxides. Of particular relevance to our study, also dealing with XO t Bu and nitroarenes, are the early works of Janzen and Guthrie, together with the more recent study by Driver. Janzen et al. studied the reaction o-and p-nitrotoluene with KO t Bu in t-butyl alcohol and DMSO and observed p,p'-dinitrobibenzyl dimer formation. p-nitrotoluene radical anion was characterised by means of EPR and proposed to be the key intermediate in the formation of the dimers, but its mechanism of formation remained unexplained. Further studies by Buncel using UV-Vis spectroscopy confirmed that the sequence consists of nitrotoluene deprotonation by the base, followed by a SET from nitrotoluene anion to nitrotoluene neutral. However, our DFT calculations predict all the steps to be endothermic for [1], (Scheme S52-S57, Table ). We also looked at a potential reduction of [1] by a deprotonated solvent molecule, finding that while this SET is exothermic, the prior deprotonation is not favoured (>25 kcal/mol, Scheme S34-45, Table ). Thus, we can confidently conclude that this mechanism does not operate the formation of [1 •-]([X + ]) in the present case.