Frankiewicz Kevin M, Willeit Nicole S, Hlukhyy Viktor, Fässler Thomas F
Department of Chemistry, TUM School of Natural Sciences, Technical University of Munich (TUM), Lichtenbergstraße 4, D-85748, Garching, Germany.
Wacker Institute of Silicon Chemistry, Technical University of Munich (TUM), Lichtenbergstraße 4, D-85748, Garching, Germany.
Nat Commun. 2024 Dec 23;15(1):10715. doi: 10.1038/s41467-024-55211-z.
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 Si clusters from the binary phase KSi, which contains both [Si] and [Si] clusters. [Si] ions, characterised by a high charge per atom ratio, behave as strong reducing agents, preventing [Si] from directed reactions. By the here reported separation of [Si] by means of fractional crystallisation, Si clusters of the precursor phase KSi are isolated as monoprotonated [SiH] 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 [HypSi] cluster.
硅是迄今为止最重要的半导体材料。然而，基于溶液的不饱和富硅分子合成方法需要效率较低的多步合成。我们报道了一种从二元相KSi直接获得可溶性多面体硅簇的方法，该二元相包含[Si]和[Si]簇。[Si]离子具有高的原子电荷比，表现为强还原剂，阻止[Si]发生定向反应。通过本文报道的分级结晶法分离[Si]，前驱体相KSi的硅簇以单质子化的[SiH]离子形式在多克规模上被分离出来，并进一步结晶为其2.2.2-穴状配体盐。通过这个两步过程可以得到20克产物——这是硅齐纳化学的一个新起点，例如三硅烷基化[HypSi]簇的分离和结构表征。
