In Martin’s reaction, the Ni(PCy3)2 complex plays the role of catalyst and the two reactants that exchange fragments are aryl fluoride and the diboron 5,5-dimethyl-1,3,2-dioxaborolane (B2nep2). Therefore, there is any reason preventing this reaction to follow a classical cross-coupling mechanism. Also, the oxidative addition and the reductive elimination as the first and last steps, respectively, seem to be well accepted. However, as mention above. the recipe contains sodium phenolate, which its role is unraveled yet. In order to understand the basics of the reaction mechanism, we outlined three possible scenarios for the transmetalation step: (a) absence of base, (b) presence of the phenolate ion, (c) participation of both the phenolate ion together with its Na+ counter-ion. Also, considering the labile character of the metal-phosphine bonds, we examined the reactivity of both mono- and bis-phosphine complexes in each reaction step.