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 [Mn^V(Sal^NMe2•)N]⁺, which facilitates N-N bond homocoupling to generate N₂, a reaction commonly observed in Mn^VI nitrides. Theoretical calculations suggest that the nitride is ambiphilic, facilitating the N-N bond formation. Notably, photoactivation of the Mn^V 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.