Isolation and Versatile Derivatization of an Unsaturated Anionic Silicon Cluster (Siliconoid)

The characteristic features of bulk silicon surfaces are echoed in the related partially substituted—and thus unsaturated—neutral silicon clusters (siliconoids). The incorporation of siliconoids into more‐extended frameworks is promising owing to their unique electronic features, but further developments in this regard are limited by the notable absence of functionalized siliconoid derivatives until now. Herein we report the isolation and full characterization of the lithium salt of an anionic R(5)Si(6)‐siliconoid, thus providing the missing link between silicon‐based Zintl anions and siliconoid clusters. Proof‐of‐principle for the high potential of this species for the efficient transfer of the intact unsaturated R(5)Si(6) moiety is demonstrated by clean reactions with representative electrophiles of Groups 13, 14, and 15.