LiN (SiMe3) 2 is found to be a suitable reagent for the selective substitution of chlorine in linear and cyclic perchloropolysilanes due to the steric bulk of the-N (SiMe3) 2 group. Starting from linear substrates, exclusively the terminally substituted amino derivatives are formed, while cyclo-Si5Cl10 and LiN (SiMe3) 2 afford the mono-and the diaminoperchlorocyclopentasilanes, respectively, depending on the stoichiometric ratio of ...