Complexation behaviour of LiCl and LiPF- model studies in the solid-state and in solution using a bidentate picolyl-based ligand.

Structural knowledge on ubiquitous lithium salts in solution and in the crystalline state is of paramount importance for our understanding of many chemical reactions and of the electrolyte behaviour in lithium ion batteries. A bulky bidentate Si-based ligand (6) was used to create simplified model systems suitable for correlating structures of LiCl and LiPF complexes in the solid-state and in solution by combining various experimental, spectroscopic, and computational methods. Solution studies were performed using H DOSY, multinuclear variable temperature NMR spectroscopy, and quantum chemical calculations. [PhSi(2-CHPy)·LiCl] (3) dissociates into a monomeric species (9) in THF. For [PhSi(2-CHPy)·LiPF] (11), low temperature NMR studies revealed an unprecedented chiral coordination mode (12) in non-coordinating solvents.