Electronic Structures and Reactivity Profiles of Aryl Nitrenoid-Bridged Dicopper Complexes
Kurtis M. Carsch, James T. Lukens, Ida M. DiMucci, Diana A. Iovan, Shao‐Liang Zheng, Kyle M. Lancaster, Theodore A. Betley
Abstract
Dicopper complexes templated by dinucleating, pacman dipyrrin ligand scaffolds (Mesdmx, tBudmx: dimethylxanthine-bridged, cofacial bis-dipyrrin) were synthesized by deprotonation/metalation with mesitylcopper (CuMes; Mes: mesityl) or by transmetalation with cuprous precursors from the corresponding deprotonated ligand. Neutral imide complexes (Rdmx)Cu2(μ2-NAr) (R: Mes, tBu; Ar: 4-MeOC6H4, 3,5-(F3C)2C6H3) were synthesized by treatment of the corresponding dicuprous complexes with aryl azides. While one-electron reduction of (Mesdmx)Cu2(μ2-N(C6H4OMe)) with potassium graphite initiates an intramolecular, benzylic C–H amination at room temperature, chemical reduction of (tBudmx)Cu2(μ2-NAr) leads to isolable [(tBudmx)Cu2(μ2-NAr)]− product salts. The electronic structures of the thermally robust [(tBudmx)Cu2(μ2-NAr)]0/– complexes were assessed by variable-temperature electron paramagnetic resonance spectroscopy, X-ray absorption spectroscopy (Cu L2,3/K-edge, N K-edge), optical spectroscopy, and DFT/CASSCF calculations. These data indicate that the formally Class IIIA mixed valence complexes of the type [(Rdmx)Cu2(μ2-NAr)]− feature significant NAr-localized spin following reduction from electronic population of the [Cu2(μ2-NAr)] π* manifold, contrasting previous methods for engendering iminyl character through chemical oxidation. The reactivity of the isolable imido and iminyl complexes are examined for prototypical radical-promoted reactivity (e.g., nitrene transfer and H-atom abstraction), where the divergent reactivity is rationalized by the relative degree of N-radical character afforded from different aryl substituents.