Faculty of Science (FNWI) - Van 't Hoff Institute for Molecular Sciences (HIMS)
Abstract
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.