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Article Abstract
Bipyridine-ligated nickel(I) and nickel(0) intermediates are widely proposed in Ni-catalyzed cross-coupling reactions. However, few isolable Ni and Ni complexes with catalytically relevant bipyridine ligands are known, limiting our understanding of these complexes' speciation and reactivity. In this work, we identify and investigate well-defined, isolable (bpy)Ni and (bpy)Ni complexes to characterize their behavior in catalytic systems. Employing spectroscopic and stoichiometric studies, we identified a solvent dependence on rates of the irreversible dimerization of (bpy)NiBr, measured rates for the activation of aryl halides and alkyl halides by (bpy)Ni and (bpy)Ni, and found that the reduction of (bpy)NiBr to Ni is inefficient with common heterogeneous metal reductants. Taken together, these studies enable us to propose a general mechanism for cross-electrophile coupling reactions.
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