Nickel–Alkyl Complexes with a Reactive PNC‐Pincer Ligand. Issue 20 (27th April 2018)

• Record Type: Journal Article
• Authors: Jongbloed, Linda S.; Vogt, Nicolas; Sandleben, Aaron; de Bruin, Bas; Klein, Axel; van der Vlugt, Jarl Ivar
• Is Part Of: European journal of inorganic chemistry. Issue 20/21(2018)
• Page Start: 2408
• Page End: 2418
• Publication Date: 2018-04-27
• Subjects: Nickel -- Pincer ligands -- Redox chemistry -- C–C reductive elimination -- Radical ions; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201800168
• Languages: English
• ISSNs: 1434-1948

Abstract

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 Ni II (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. Abstract : Two Ni II (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, while one‐electron reduction results in a ligand‐centered radical anion. This further attenuates the breadth of chemical reactivity offered by such PNC‐pincer ligands.