Four heteroleptic copper(I) complexes containing phenanthroline and monoanionic nido-carborane-diphosphine ligands have been prepared and structurally characterized by various spectroscopic techniques and X-ray diffraction. These complexes exhibit intense absorptions in the visible range and excited-state lifetimes on the microsecond scale. Their application in visible-light-induced cross-dehydrogenative coupling reactions was investigated. Preliminary studies showed that one of the four copper(I) complexes is an efficient catalyst for photoinduced oxidative C H functionalization using oxygen as oxidant. Furthermore, α-functionalized tertiary amines were obtained in good-to-excellent yields by light irradiation ( λ>420 nm) of a mixture of our Cu I complex, tertiary amines, and a variety of nucleophiles (nitroalkane, acetone, or indoles) under aerobic conditions. Electron paramagnetic resonance measurements provided evidence for the formation of superoxide radical anions (O 2−⋅) rather than singlet oxygen ( 1O 2) during these photocatalytic reactions. Chemistry - A European Journal, 2014 Synthesis and chemical structures of Cu1–Cu4. X-ray crystal structure of Cu2. Perspective view with thermal ellipsoids drawn at the 30 % probability level. Hydrogen atoms and solvent molecules have been omitted for clarity. |