Making Carbon–Chlorine Bonds by Dipalladium Electrocatalysis



[(Benzo[h]quinolinyl)PdII(μ-OAc)]2 and [(2-phenylpyridinyl)PdII(μ-OAc)]2 undergo one-electron oxidation to afford mixed-valent (PdII–PdIII) species. Electrochemical oxidation of the PdII–PdII complexes in the presence of chloride at the PdIII–PdII/PdII–PdII potential results in a two-electron loss with addition of two chlorides to form [(benzo[h]quinolinyl)PdIIICl(μ-OAc)]2 and [(2-phenylpyridinyl)PdIIICl(μ-OAc)]2, respectively. When both excess benzo[h]quinoline and chloride are present, [(benzo[h]quinolinyl)PdII(μ-OAc)]2 electrocatalyzes the chlorination of the substrate to afford 10-chlorobenzo[h]quinoline with high chemical and Faradaic yields.