Enolizations of 2-methylcyclohexanone by lithium hexamethyldisilazide (LiHMDS) in the presence of three chelating ligands--trans-N,N,N',N'-tetramethylcyclohexanediamine, N,N,N',N'-tetramethylethylenediamine, and dimethoxyethane--reveal an approximate 40-fold range of rates. NMR spectroscopic analyses and rate studies reveal isostructural transition structures based on monomeric LiHMDS for the diamines. Rate studies of LiHMDS/dimethoxyethane-mediated enolizations implicate a substantial number of monomer and dimer-based mechanisms. The rate laws vary for the three ligands because of ligand-de pendent structural differences in both the reactants and the transition structures. The importance of LiHMDS-ketone complexes and the role of hydrocarbon cosolvents are discussed.