A rigorous dive into the precise mechanistic intricacies of this new protocol is beyond the scope of this report. However, several experiments were performed to support the hypothesized high-level mechanistic picture that is outlined in Figure . The basic elementary mechanistic steps are postulated to be as follows: 1. Deposition of Ag nanoparticles onto the cathode as extensively studied previously, Reductive elimination to form the quaternary center or the isomeric product. Although a concerted oxidative addition is commonly proposed, a stepwise oxidative addition process cannot be ruled out at this time. In support of the above, three diagnostic studies were performed (panels I-III). The optimum ratio of pyridine to Ni-complex was assessed by carrying out several reactions, with varying amounts of pyridine and a fixed amount of (S)-BINAP-Ni(II) complex (Figure , panel I). An optimum ratio of between 3-4 equivalents of pyridine relative to the Ni(II) complex was observed. When more equivalents of pyridine were added to the reaction, a lower yield was observed, indicating that the over-complexation of pyridine with Ni may lead to catalyst deactivation. In order to rationalize the role that pyridine plays in the cross coupling, cyclic voltammetry (CV) experiments were conducted with varying amounts of pyridine (Figure , panel II). The CV of (BINAP)NiCl2 did not show any relevant redox activity. However, the titration of 1-4 equivalents of pyridine resulted in the development of a new irreversible reduction peak at -1.3 V. The intensity of this new reduction peak increases with increasing the amount of pyridine. This peak has been assigned to Ni(I) species by Amatore and his collaborators in their studies of electrochemical reduction of bidentate-phosphine ligated NiCl2 complexes. Therefore, we hypothesize in the presence of pyridine, the formation of a (BINAP)Ni(0) is minimized, and active pyridine-stabilized Ni(I) species are sustained during the reaction. Along the same line, the enhanced efficiency of the cross-coupling at a higher NiCl2 loading relative to (S)-BINAP (5:1 ratio, Table ), may be necessary to maintain an increased concentration of active Ni(I) species.