LiHMDS-mediated enolizations of 2-methylcyclohexanone in toluene/polydentate ligand mixtures are described. ⁶Li and ¹⁵N NMR spectroscopies and in situ IR spectroscopy were used to characterized and monitor reactants. Rate studies reveal that enolizations by LiHMDS in TMEDA, TMCDA, and DME proceed by LiHMDS monomers. Studies of the enolization also reveal an inverse dependence on DME concentration and a zero order dependence on TMEDA and TMCDA concentration. Hydrocarbon effects on the rate of enolization in TMEDA were also investigated.