A stable Nickel(II) methyl complex containing a diphosphinoboryl (PBP) pincer ligand is described. Mechanistic studies on the hydrogenolysis of the Ni-Me bond suggest a metal ligand cooperation mechanism that involves the intermediacy of a σ-B‒H Ni(0) species that further undergoes B‒H oxidative addition to form a Ni(II) hydride complex.