Cyclometalated Nickel Complexes as Key Intermediates in C(sp2)–H Bond Functionalization: Synthesis, Catalysis, Electrochemical Properties, and DFT Calculations

This paper elucidates the redox properties and reactivity of a number of cyclometalated nickel­(II) complexes in oxidation processes. Original and robust procedures for the synthesis of nickelacycles with two cyclometalated moieties and halogenated nickelacycles were developed. The complexes were studied by means of electrochemical, ESR, DFT, and single-crystal XRD methods. Notable features of the nickelacycles are unusually low oxidation potentials. Upon electrochemical oxidation the complexes produce carbon–carbon and carbon–heteroatom coupled products, the ratio of which can be tuned by the conditions applied.