Manipulating the Substituent Sphere of a Bicyclic Silicon(I) Ring Compound Results in Anionic Cubane‐Type Clusters and a Tetrahedral Silanide

The silicon(I) ring compound Si4{N(SiMe3)Mes}4 can be reduced by using KC8 in the presence of [18]crown-6 under abstraction of four amido substituents. This results after dimerization in the first dianionic octasilacubane-type compound with four unsubstituted silicon atoms. DFT calculations revealed that it exhibits a four-center–six-electron bond with electron density inside the cube. Further derivatizations of the silicon(I) ring compound with KC8 in the absence of [18]crown-6 but using trapping reagents results in more and different anionic silicon based clusters. More information can be found in the Research Article by F. Lips and co-workers (DOI: 10.1002/chem.202400368).