1. Multiconfigurational Electronic Structure of Nickel Cross-Coupling Catalysts Revealed by X-ray Absorption Spectroscopy.
- Author
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Nelson, Kacie, Kazmierczak, Nathanael, Cagan, David, Follmer, Alec, Scott, Thais, Raj, Sumana, Garratt, Douglas, Powers-Riggs, Natalia, Gaffney, Kelly, Hadt, Ryan, and Cordones, Amy
- Abstract
NiII 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)(RAr)Cl (R = MeOOC, t-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 L2,3-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 ab initio 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.
- Published
- 2024