Herein, we report the utilization of Ni–Ni species as a manifold for enabling a “ring-walking” event by dynamic translocation of the metal center over the arene backbone. Experimental and computational studies support a translocation occurring via a 1,2-hydride shift. The synthetic applicability of the method is illustrated in a series of C–C bond formations that occur at distal C(sp2)–H sites of simple aryl pivalates.