RESUMO
Perfluoroalkyl iodides generally formed electron donor-acceptor (EDA) complexes by halogen bonding with a nitrogen atom containing Lewis bases. Since the electronegativity of the oxygen atom is stronger than that of the nitrogen atom, the resulting Rf-I···O-type halogen bonding EDA complex is less inclined to undergo electron transfer. Here, we reported rare ternary EDA complexes among perfluoroalkyl iodide, oxygen atom, and base. Mechanism experiments and density functional theory theoretical (DFT) calculations indicated that a base-promoted proton-coupled electron transfer (PCET) process was involved in this photochemical reaction. The intracomplex electron transfer event generated two radical species, perfluoroalkyl radical and TEMPO radical, enabling the subsequent oxy-perfluoroalkylation of olefins.