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Electronic Structures and Reactivity Profiles of Aryl Nitrenoid-Bridged Dicopper Complexes
Kurtis M Carsch1, James T Lukens2, Ida M DiMucci2
1Department of Chemistry and Chemical Biology , Harvard University , 12 Oxford Street , Cambridge , Massachusetts 02138 , United States.
Abstract:
Dicopper complexes templated by dinucleating, pacman dipyrrin ligand scaffolds (Mesdmx, dmx: 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, Bu; 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 (dmx)Cu2(μ2-NAr) leads to isolable [(dmx)Cu2(μ2-NAr)]- product salts. The electronic structures of the thermally robust [(dmx)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.
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