Stable unsaturated silicon clusters (siliconoids).

Unsaturated silicon clusters are key intermediates of silicon deposition processes from the gas phase, which is reflected in the recently introduced term "siliconoids" for silicon rich clusters with at least one hemispheroidally coordinated vertex. Unlike the case of metalloid clusters of heavier Group 14 elements, stable homonuclear derivatives containing silicon have become available just recently. This review summarizes the developments since the first report on a stable unsaturated silicon cluster in 2005. The synthesis, structure and reactivity under retention of the unsaturated vertices (i.e. the functionalization) of stable siliconoids is discussed within the broader context of soluble Zintl anions of silicon and metalloid clusters. A structural parameter is introduced as a quantitative measure to characterize the "hemispheroidality" of an unsubstituted vertex of a siliconoid.