Polydentate Amine and Ether Solvates of Lithium Hexamethyldisilazide (LiHMDS): Relationship of Ligand Structure, Relative Solvation Energy, and Aggregation State

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6 Li, 15 N, and 13 C NMR spectroscopic investigations of [ 6 Li, 15 N]lithium hexamethyldisilazide ([ 6 Li, 15 N]LiHMDS) coordinated by 29 polyamines, polyethers, and aminoethers reveal a range of structural types including η 1 -coordinated mono- and disolvated dimers, η 2 -coordinated (3-coordinate) monomers, η 1,η 2 -coordinated (4-coordinate) monomers, η 2,η 2 -coordinated (5-coordinate) monomers, polymers (linked dimers), triple ions, and solvent-separated ion pairs. Ligand binding constants on the LiHMDS monomers shed light on chelate ring size and steric effects, aza- and oxaphilicity, mechanisms and rates of ligand substitution, and the “macrocyclic effect.”