Recently, there have been several investigations into Ni-catalyzed Suzuki-Miyaura cross-coupling reactions, presumably due its growing popularity as a powerful alternative to Pd-catalyzed reactions. However, nickel catalysis can access various different reaction mechanisms based on the catalytic system in question. Typically, Ni(0)/Ni(II) catalytic cycles are proposed when phosphine ligands are employed, while Ni(I)/Ni(III) cycles are proposed for reactions with N-heterocyclic carbene and pincer-type ligands. The involvement of single electron transfer (SET) processes was experimentally examined by adding catalytic amounts of 2,6-di-tert-butyl-4methylphenol (BHT) as a radical inhibitor to both the (Z)-and (E)-selective diastereodivergent conditions. In each case, the reactions were unaffected by the presence of the inhibitor (see SI for details). This observation is also supported by our DFT calculations, which suggest that Ni(0)/Ni(II) complexes are energetically favored in participating in oxidative addition, transmetalation, and reductive elimination as compared to their open-shell Ni(I)/Ni(III) counterparts (see SI for details). Hence, only the closed-shell Ni(0)/Ni(II) mechanisms of oxidative addition, transmetalation, and reductive elimination were investigated further with ligands L1 and L2.