Synthesis and functionalization of the six-vertex anionic amido-substituted silicon cluster [Si 6 {N(SiMe 3 )Ph} 5 ] .

The reaction of the six-vertex amido-substituted silicon cluster Si 6 {N(SiMe 3 )Ph} 6 1 with two equiv. of KC 8 results in the abstraction of K{N(SiMe 3 )Ph} and leads to the contact ion pair 2 including an anionic silicon cluster with two unsubstituted pyramidal vertices. Facile functionalization of 2 was achieved with MeI, SiCl 4 and SiBr 4 and results in neutral two-fold functionalized silicon clusters.