Nickel–Alkyl Complexes with a Reactive PNC‐Pincer Ligand

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 Ni(II)(PNC) complexes featuring either a methyl (2CH(3)) or CF(3) co‐ligand (2CF(3)) 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.