Exploring the solid state and solution structural chemistry of the utility amide potassium hexamethyldisilazide (KHMDS)

Abstract

The structural chemistry of eleven donor complexes of the important Brønsted base potassium 1,1,1,3,3,3-hexamethyldisilazide (KHMDS) has been studied. Depending on the donor, each complex adopted one of five general structural motifs. Specifically, in this study the donors employed were toluene (to give polymeric 1 and dimeric 2), THF (polymeric 3), N,N,N′,N′-tetramethylethylenediamine (TMEDA) (dimeric 4), (R,R)-N,N,N′,N′-tetramethyl-1,2-diaminocyclohexane [(R,R)-TMCDA] (dimeric 5), 12-crown-4 (dimeric 6), N,N,N′,N′-tetramethyldiaminoethyl ether (TMDAE) (tetranuclear dimeric 8 and monomeric 10), N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) (tetranuclear dimeric 7), tris[2-dimethyl(amino)ethyl]amine (Me6TREN) (tetranuclear dimeric 9) and tris{2-(2-methoxyethoxy)ethyl}amine (TMEEA) (monomeric 11). The complexes were also studied in solution by 1H and 13C NMR spectroscopy as well as DOSY NMR spectroscopy.