[(K,Rb)@([2.2.2]crypt)]2(K,Rb)4[Si9W(CO)4] ⋅ 13.4 NH3 – The First Tungsten Functionalized Silicon Zintl Cluster.

The reaction between the heteroleptic metal carbonyl complex [W(CO)4(tmeda)] ((tmeda)=N,N,N′,N′‐Tetramethylethane‐1,2‐diamine) with [Si9]4− silicon Zintl clusters in presence of [2.2.2]crypt ([2.2.2]crypt=4,7,13,16,21,24‐Hexaoxa‐1,10‐diazabicyclo[8.8.8]‐hexacosane) in liquid ammonia yielded the compound [(K,Rb)@([2.2.2]crypt)]2(K,Rb)4[Si9W(CO)4] ⋅ 13.4 NH3. The compound was analyzed by single crystal X‐ray diffraction and crystallizes in the space group P1‾ ${P\bar{1}}$ (a=11.48390(10) Å, b=19.7383(2) Å, c=19.8983(2) Å, α=112.5760(10)°, β=97.4210(10)°, γ=95.3760(10)°, V=4079.01(7) Å3). The compound represents the first group 6 carbonylate‐functionalized silicon Zintl cluster. The central moiety is composed of a tricapped trigonal prismatic nine‐atom silicon species which coordinates with the lone pair of one capping atom to the tungsten tetracarbonylate, forming a pseudo trigonal bipyramidal carbonylate cluster anion [Si9W(CO)4]6−. The chemical bonding in the new cluster entity is analyzed using theoretical calculations and subsequent analysis using QTAIM and NBO. [ABSTRACT FROM AUTHOR]