Considering the electron rich nature of the aryl iodide of deprotonated 1, we believe that it undergoes a concerted dissociative SET reduction (meaning there will be no radical dianion intermediate) following the Marcus Savéant theory, directly affording the aryl radical intermediate . Density Functional Theory (DFT) calculations revealed that the most favorable SET donor present would be the deprotonated product BASN -(See section 6.12 of SI). Time Dependent Density Functional Theory (TD-DFT) analysis of BASN -s longest wavelength excitation of revealed a   * transition involving charge transfer from the electron rich aniline moiety across the entire electron poor biaryl moiety (Figure ); such a charge transfer is reminiscent of a typical organophotocatalyst excitation .