Li-6, N-15, and C-13 NMR spectroscopic investigations of [Li-6, N-15]lithium hexamethyldisilazide ([Li-6, N-15]LiHMDS) coordinated by 29 polyamines, polyethers, and aminoethers reveal a range of structural types including eta(1)-coordinated mono- and disolvated dimers, eta(2)-coordinated (3-coordinate) monomers, eta(1),eta(2)-coordinated (4-coordinate) monomers, eta(2),eta(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."