On the Reactivity of NHC t Bu AuCl towards Rb 6 Cs 6 Si 17 : The First Gold‐Silicon Cluster [(NHC t Bu Au) 6 (η 2 ‐Si 4 )]Cl 2 ·7NH 3 and an Imide Capped Gold Triangle (NHC t Bu Au) 3 NHCl

Crystals of the two new compounds (NHC t Bu Au) 3 NHCl and [(NHC t Bu Au) 6 (η 2 ‐Si 4 )]Cl 2 · 7NH 3 could be isolated from the reaction of Rb 6 Cs 6 Si 17 with NHC t Bu AuCl in the presence of [2.2.2]‐cryptand in liquid ammonia. Both compounds were characterized by single‐crystal X‐ray diffraction and crystallize trigonally without any alkali metals or chelating ligands. Additionally, the crystal of [(NHC t Bu Au) 6 (η 2 ‐Si 4 )]Cl 2 · 7NH 3 was further interpreted by means of ELF and NBO calculations. In the case of (NHC t Bu Au) 3 NHCl, NMR experiments provided an exceptional insight into the reaction processes in solution and allowed for the detection of sequential precursors. In the class of capped gold triangles (NHC t Bu Au) 3 NHCl impresses with its unique characteristics of being capped by an imide and bound to N ‐heterocyclic carbenes as ligands instead of the ubiquitously employed phosphines. The gold capped silicon tetrahedron [(NHC t Bu Au) 6 (η 2 ‐Si 4 )]Cl 2 · 7NH 3 represents the first known silicide‐gold compound, as well as the first known functionalized Zintl anion, crystallized with a cationic central moiety.