Copper(I) SNS pincer complexes: Impact of ligand design and solvent coordination on conformer interconversion from spectroscopic and computational studies

[Display omitted] •Syntheses and characterizations of novel Cu(I)-SNS pincer compounds are reported.•NMR spectroscopy indicates fluxionality of the SNS pincer.•VT NMR spectra permit thermodynamic analysis of the fluxionality.•DFT modeling supports a solvent-mediated hemilability of the SNS pincer. The syntheses and detailed characterizations (X-ray crystallography, NMR spectroscopy, cyclic voltammetry, infrared spectroscopy, electrospray mass spectrometry, and elemental analyses) of two new Cu(I) pincer complexes are reported. The pincer ligand coordinates through one nitrogen and two sulfur donor atoms and is based on bis-imidazole or bis-triazole precursors. These tridentate SNS ligands incorporate pyridine and thione-substituted imidazole or triazole functionalities with connecting methylene units that provide flexibility to the ligand backbone and enable high bite-angle binding. Variable temperature 1H NMR analysis of these complexes and of a similar zinc(II) SNS system shows that all are fluxional in solution and permits the determination of ΔGexp‡ and ΔSexp‡. DFT calculations are used to model the fluxionality of these complexes and indicate that a coordinating solvent molecule can promote hemilability of the SNS ligand by lowering the energy barrier involved in the partial rotation of the methylene units.