Multiconfigurational Electronic Structure of Nickel Cross-Coupling Catalysts Revealed by X-ray Absorption Spectroscopy

Ni^II 2,2'-bipyridine complexes are commonly invoked intermediates in metallaphotoredox cross-coupling reactions. Despite their ubiquity, design principles targeting improved catalytic performance remain underdetermined. A series of Ni(^Rbpy)(^{R^'}Ar)Cl (R = MeOOC, <i>t</i>-Bu, R' = CH₃, CF₃) complexes were proposed to have multiconfigurational electronic structures on the basis of multiconfigurational/multireference calculations, with significant mixing of Ni → bpy metal-to-ligand charge transfer (MLCT) configurations into the ground-state wave function. Here, Ni K-edge and L_2,3-edge X-ray absorption spectroscopies provide experimental support for the highly covalent and multiconfigurational electronic structures of these complexes. The pre-edge intensity in the K-edge spectrum reflects highly covalent Ni-aryl bonding. The L₃-edge spectral shape is dependent on ligand functionalization, and a feature reflecting the MLCT character is assigned using prior <i>ab initio</i> and new semiempirical calculations. The results suggest the push/pull effects of the aryl/bpy ligands moderate the changes in electron density on Ni during the multiredox cross-coupling reaction cycle.