Intramolecular redox-active ligand-to-substrate single-electron transfer: Radical reactivity with a palladium(II) complex

Coordination of the redox-active tridentate NNO ligand L^H2 to Pd^II yields the paramagnetic iminobenzosemiquinonato complex 3. Single-electron reduction of 3 yields diamagnetic amidophenolato complex 4, capable of activating aliphatic azide 5. Experimental and computational studies suggest a redox-noninnocent pathway wherein the redox-active ligand facilitates intramolecular ligand-to-substrate single-electron transfer to generate an open-shell singlet nitrene-substrate radical, ligand radical , enabling subsequent radical-type C-H amination reactivity with Pd^II.