Syntheses and 1 H NMR Spectra of Substituted Zintl Ions [Ge 9 R n ] (4– n )– : Crystal Structures of [Ge 9 R] 3– (R = 2,4,6‐Me 3 C 6 H 2 , CHCH 2 ) and Indication of Tris‐Vinylated Clusters

The introduction of a mesityl (Mes; 2,4,6‐Me 3 C 6 H 2 ) ligand to a Ge 9 polyanion is accomplished by the reaction of [Ge 9 ] 4– solutions with Ag 4 Mes 4 . The crystal structure investigation of its [K([2.2.2]crypt)] salt ([2.2.2]crypt: 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane) shows that [Ge 9 Mes] 3– comprises one exo ‐bonded aryl ligand in accordance with the 1 H NMR spectroscopic data. The formation of mono‐, bis‐, and tris‐substituted Zintl Ions [Ge 9 R n ] (4– n )– ( n = 1, 2, and 3; R = CHCH 2 ) is investigated by 1 H NMR spectroscopy. The mono‐ and bis‐vinylated Ge 9 clusters, [Ge 9 (CHCH 2 )] 3– and [Ge 9 (CHCH 2 ) 2 ] 2– , were obtained by the reaction of K 4 Ge 9 with Me 3 SiC≡CSiMe 3 in ethylenediamine. In the presence of [18]crown‐6 (1,4,7,10,13,16‐hexaoxacyclooctadecane) and K(C 5 H 5 ) crystals containing both cluster species were isolated and structurally characterized as[K([18]crown‐6)] 2 {(η 5 ‐C 5 H 5 )[K([18]crown‐6)] 2 }[Ge 9 (CHCH 2 )]and [K([18]crown‐6)]{(η 5 ‐C 5 H 5 )[K([18]crown‐6)] 2 }[Ge 9 (CHCH 2 ) 2 ], respectively. 1 H NMR experiments hint for the tris‐vinylated cluster [Ge 9 (CHCH 2 ) 3 ] – .