A detailed mechanistic evaluation of the Ni(IPr)2-catalyzed [2+2+2]-cycloaddition of diynes and nitriles was 2 conducted. Through kinetic analysis of these reactions, observed regioselectivities of the products, and stoichiometric reactions, Ni(IPr)2-catalyzed cycloadditions of diynes and nitriles appear to proceed by a heterooxidative coupling mechanism, contrary to other common cycloaddition catalysts. Reaction profiles demonstrated strong dependence in nitrile, resulting in variable nitrile-dependent resting states. Strong coordination and considerable steric bulk of the carbene ligands facilitate selective initial binding of nitrile thereby forcing a heterocoupling pathway. In situ IR data suggests the initial binding of the nitrile resides in a rare, η1-bound conformation. Following nitrile coordination are a rate-determining hapticity shift of the nitrile and subsequent loss of carbene. Alkyne coordination then leads to heterooxidative coupling, insertion of the pendant alkyne, and reductive elimination to afford pyridine products.