Synthesis and Structure of a Metal‐Rich Tetradecagallium Cluster with a Polyhedral Core

Ga 14 (hypersilyl) 6 [hypersilyl = Si(SiMe 3 ) 3 ] is a novel metal‐rich and polyhedral cluster compound with an unprecedented structure in gallium chemistry. The gallium atoms form an omnicapped cube, meaning six gallium hypersilyl units are capping the faces of a Ga 8 cube. The synthesis of the cluster is performed using a new reagent, a solution of subvalent gallium trifluoromethanesulfonate, which is easily obtained by oxidation of gallium with silver trifluoromethanesulfonate in toluene. After the addition of an excess of lithium hypersilanide and warming up the reaction mixture, [Ga 14 (hyp) 6 ] is isolated by crystallization from n ‐hexane and structurally characterized by single crystal X‐ray crystallography. density functional theory calculations confirmed structural variations of the core structure of Ga 14 R 6 depending on numbers of cluster electrons and types of substituents.