Based on previous work related to the design and application of rigid tridentate phosphine-pyridine-phenyl coordination offered by a PNC-pincer ligand upon cyclometalation to nickel, the synthesis, spectroscopic and solid state characterization and redox-reactivity of two NiII(PNC) complexes featuring either a methyl (2CH3 ) or CF3 co-ligand (2CF3 ) are described. One-electron oxidation is proposed to furnish C-C reductive elimination, as deduced from a combined chemical, electrochemical, spectroscopic and computational study. One-electron reduction results in a ligand-centered radical anion, as supported by electrochemistry, UV spectroelectrochemistry, EPR spectroscopy, and DFT calculations. This further attenuates the breadth of chemical reactivity offered by such PNC-pincer ligands.
Keywords: C–C reductive elimination; Nickel; Pincer ligands; Radical ions; Redox chemistry.