Detailed kinetic studies of the reaction of a model Ni-0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [(NiX)-X-I(dppf)] (and biaryl) or [Ni-II(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to Ni-I products in kinetic experiments conditions. produce more homocoupling products under catalytic conditions.