Cu(I) Complexes of Pincer Pyridine-Based N-Heterocyclic Carbenes with Small Wingtip Substituents: Synthesis and Structural and Spectroscopic Studies

Six new Cu(I) complexes with pincer N-heterocyclic carbene (NHC) ligands of the type 2,6-bis(3-alkylimidazol-2-ylidene)pyridine, I(R)CNC, and 2,6-bis(3-alkylimidazol-2-ylidene)methylpyridine, I(R)C^N^C, where R = Me, Et, and iPr have been synthesized using Cu precursors and bis(imidazolium) salts. All of these compounds, namely, [Cu2(IMeCNC)2](PF6)2, 1; [Cu2(IEtCNC)2](PF6)2, 2; [Cu2(IiPrCNC)2](PF6)2, 3; [Cu(IMeC^N^C)](PF6), 4; [Cu(IEtC^N^C)](PF6), 5; and [Cu(IiPrC^N^C)](PF6), 6, have been characterized by 1H and 13C NMR spectroscopies, elemental analysis, solution conductivity, and electrochemical studies. Single crystal X-ray structures were obtained for all complexes except 1. The crystallographic data reveal a binuclear structure containing two Cu atoms at a close distance, 2.622–2.811 A for all the complexes except 5, which shows a unique mononuclear structure. Spatial syn arrangement of ethyl groups and extensive π–π stacking in the solid state accounts for the mononuclear structure of complex 5. A p...