Photogenerated Ni(I)-Bipyridine Halide Complexes: Structure-Function Relationships for Competitive C(sp 2 )-Cl Oxidative Addition and Dimerization Reactivity Pathways.

We report the facile photochemical generation of a library of Ni(I)-bpy halide complexes (Ni(I)( R bpy)X (R = t -Bu, H, MeOOC; X = Cl, Br, I) and benchmark their relative reactivity toward competitive oxidative addition and off-cycle dimerization pathways. Structure-function relationships between the ligand set and reactivity are developed, with particular emphasis on rationalizing previously uncharacterized ligand-controlled reactivity toward high energy and challenging C(sp 2 )-Cl bonds. Through a dual Hammett and computational analysis, the mechanism of the formal oxidative addition is found to proceed through an S N Ar-type pathway, consisting of a nucleophilic two-electron transfer between the Ni(I) 3 d ( z 2 ) orbital and the C aryl -Cl σ* orbital, which contrasts the mechanism previously observed for activation of weaker C(sp 2 )-Br/I bonds. The bpy substituent provides a strong influence on reactivity, ultimately determining whether oxidative addition or dimerization even occurs. Here, we elucidate the origin of this substituent influence as arising from perturbations to the effective nuclear charge ( Z eff ) of the Ni(I) center. Electron donation to the metal decreases Z eff , which leads to a significant destabilization of the entire 3 d orbital manifold. Decreasing the 3 d ( z 2 ) electron binding energies leads to a powerful two-electron donor to activate strong C(sp 2 )-Cl bonds. These changes also prove to have an analogous effect on dimerization, with decreases in Z eff leading to more rapid dimerization. Ligand-induced modulation of Z eff and the 3 d ( z 2 ) orbital energy is thus a tunable target by which the reactivity of Ni(I) complexes can be altered, providing a direct route to stimulate reactivity with even stronger C-X bonds and potentially unveiling new ways to accomplish Ni-mediated photocatalytic cycles.