An efficient multi-gram access in a two-step synthesis to soluble, nine-atomic, silylated silicon clusters

Silicon is by far the most important semiconducting material. However, solution-based synthetic approaches for unsaturated silicon-rich molecules require less efficient multi-step syntheses. We report on a straightforward access to soluble, polyhedral Si9 clusters from the binary phase K12Si17, which contains both [Si4]4− and [Si9]4− clusters. [Si4]4− ions, characterised by a high charge per atom ratio, behave as strong reducing agents, preventing [Si9]4− from directed reactions. By the here reported separation of [Si4]4− by means of fractional crystallisation, Si9 clusters of the precursor phase K12Si17 are isolated as monoprotonated [Si9H]3− ions on a multi-gram scale and further crystallised as their 2.2.2-Cryptate salt. 20 grams of the product can be obtained through this two-step procedure - a new starting point for silicon Zintl chemistry, such as the isolation and structural characterisation of a trisilylated [MeHyp3Si9]− cluster.