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.

中文翻译：

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具有反应性 PNC 钳状配体的镍-烷基配合物

基于 PNC 钳状配体提供的刚性三齿膦-吡啶-苯基配位在环金属化成镍时的设计和应用的相关工作，两种 NiII(PNC) 配合物的合成、光谱和固态表征以及氧化还原反应性描述了具有甲基 (2CH3) 或 CF3 共配体 (2CF3) 的特征。根据化学、电化学、光谱和计算研究的结合，提出了单电子氧化来提供 C-C 还原消除。电化学、紫外光谱电化学、EPR 光谱和 DFT 计算支持单电子还原产生以配体为中心的自由基阴离子。这进一步减弱了这种 PNC 钳状配体提供的化学反应的广度。