Aggregation and Solvation of n-Butyllithium

Solution characterizations and ligand binding constants were determined for n-butyllithium in hydrocarbon and ethereal solvents using diffusion-ordered NMR. In hydrocarbon solvents, n-butyllithium exists primarily as an octamer at -40 °C and deaggregates to a hexamer when the temperature is increased. In the presence of THF or diethyl ether, n-butyllithium exists predominantly as a tetra-solvated tetramer and deaggregates to a tetra-solvated dimer in the presence of a large excess or neat THF. The ligand binding constants for the tetra-solvated tetramers were measured using ¹H NMR/DOSY titration.