European Journal of Inorganic Chemistry 2018-03-15

Nickel‐alkyl complexes with a reactive PNC‐pincer ligand

Linda Stéphanie Jongbloed; Nicolas Vogt; Aaron Sandleben; Bas de Bruin; Axel Klein; Jarl Ivar van der Vlugt

Index: 10.1002/ejic.201800168

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Abstract

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.