Terminal Copper Nitrenoid Formation and Reactivity Induced by Absorption to an Antenna Ligand

Copper nitrenoids are key intermediates in copper-catalyzed direct C-H amination reactions. Further development of this important reaction relies on knowing the properties and reactivity of the nitrenoid intermediates. This work utilizes antenna ligands to form copper nitrenoid complexes and monitor the consecutive C-H amination reactions under well-defined single-molecule conditions in the gas phase. The [Cu(L^photo)(L^azide)]⁺ precursors (L^photo is a bidentate antenna ligand, and L^azide is an organic azide) were stored in an ion trap at 3.5 K and irradiated by visible light, which resulted in denitrogenation of the complex. Further irradiation of the copper nitrenoid led to the consecutive C-H amination of the antenna ligand. The nitrenoid complexes, as well as the products of the C-H amination, were characterized by helium tagging IRPD spectroscopy, and the mechanism was described by DFT calculations. This research demonstrates that the antenna ligands can be used to promote the denitrogenation of metal azides in the gas phase and also channel the internal energy to promote further reactivity, which opens a new way to study the reactivity of highly reactive species under well-defined conditions.