Dedicated to Professor Cameron Jones on the occasion of his 60th birthday.The metalloid cluster [Ge 9 (Hyp tBuPh2 ) 3 ]K (1) (Hyp tBuPh2 =Si-(SiMe 3 ) 2 (SitBuPh 2 )) is obtained through three different reaction courses. These are the disproportionation reaction of Ge I Br and subsequent substitution of the bromine atoms, the reaction of the germanium subhalide cluster Ge 14 Br 8 (PEt 3 ) 4 with KHyp tBuPh2 and the reaction of the Zintl phase K 4 Ge 9 with ClHyp tBuPh2 . The different reaction courses are described, together with the characterization and follow-up reaction of the new metalloid cluster 1.

LiEC(SiMe3)3 (E = Se, Te) acts as a donor of chalcogen atoms and as a substituent to give binary [(RxGey)Ez] cage compounds by the reaction with GeCl2·dioxane. These cage compounds show unique structural features within Ge/E cage compounds.