Synthesis of Bis(pentafluoroethyl)germanes

The chemistry of bis(pentafluoroethyl)germanes (C 2 F 5 ) 2 GeX 2 is presented. The synthesis of such species requires Br 2 GePh 2 , wherein the phenyl substituents function as suitable protecting groups. After treatment with two equivalents of LiC 2 F 5 , (C 2 F 5 ) 2 GePh 2 is produced. The replacement of the phenyl rings is smoothly effected by gaseous HBr or HCl in the presence of a Lewis acidic catalyst. The trigermoxane [(C 2 F 5 ) 2 GeO] 3 results from the reaction of (C 2 F 5 ) 2 GeBr 2 with Ag 2 CO 3 . Its crystalline 1,10‐phenanthroline adduct was fully characterised by X‐ray diffraction. The combination of (C 2 F 5 ) 2 GeBr 2 with Bu 3 SnH gave rise to the formation of (C 2 F 5 ) 2 GeH 2 .