Monovalent Nickel-Mediated Radical Formation: A Concerted Halogen-Atom Dissociation Pathway Determined by Electroanalytical Studies

The recent success of nickel catalysts in stereoconvergent cross-coupling and cross-electrophile coupling reactions partly stems from the ability of monovalent nickel species to activate C(sp³) electrophiles and generate radical intermediates. This electroanalytical study of the commonly applied (bpy)Ni catalyst elucidates the mechanism of this critical step. Data rule out outer-sphere electron transfer and two-electron oxidative addition pathways. The linear free energy relationship between rates and the bond-dissociation free energies, the electronic and steric effects of the nickel complexes and the electrophiles, and DFT calculations support a variant of the halogen-atom abstraction pathway, the inner-sphere electron transfer concerted with halogen-atom dissociation. This mechanism accounts for the observed reactivity of different electrophiles in cross-coupling reactions and provides a mechanistic rationale for the chemoselectivity obtained in cross-electrophile coupling over homocoupling.