C–H Bond Activation via Photolysis of a Mn Nitride Ligand Radical Complex

We report the thermal and photoactivation of a solution-stable Mn nitride ligand radical complex [MnV(SalNMe2•)N]+, which facilitates N–N bond homocoupling to generate N2, a reaction commonly observed in MnVI nitrides. Theoretical calculations suggest that the nitride is ambiphilic, facilitating the N–N bond formation. Notably, photoactivation of the MnV ligand radical at room temperature enables rapid C–H bond activation, leading to the formation of C–N insertion products, excluding dihydroanthracene where a desaturation product is observed. This study presents a rare example of photochemically driven intermolecular N atom transfer to a C–H bond mediated by a first-row Mn terminal nitride complex, made possible by the unique stability and turn-on reactivity of the oxidized ligand radical electronic structure.