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

Abstract

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.