Tetrasilatetrahedranide: A Silicon Cage Anion

The first silicon cage anion, tris{bis[bis(trimethylsilyl)methyl](methyl)silyl}tetrasilatetrahedranide (6-), has been synthesized by the reaction of tetrakis{bis[bis(trimethylsilylmethyl](methyl)silyl}tetrasilatetrahedrane with potassium graphite in diethyl ether by reductive cleavage of exocyclic Si−Si bond. The structural characterization of K+(18-crown-6)·6- has been achieved by X-ray crystallography, showing that 6- is a separated ion pair and the tetrasilatetrahedranide moiety has a significantly distorted tetrahedrane skeleton containing one inverted tetrahedral (umbrella type) silicon atom. The four silicon atoms in the Si4 skeleton are equivalent on the NMR time scale due to the migration of the Dis2MeSi substituent.