Owing to the highly electron-withdrawing C 2 F 5 groups, the tris(pentafluoroethyl)germane (C 2 F 5 ) 3 GeH represents an interesting Brønsted acidic compound. The germane is accessible by the treatment of the corresponding halogenogermanes( C 2 F 5 ) 3 GeX (X = Cl, Br) with Bu 3 SnH. After clarifying its molecular structure in the solid state by X-ray diffraction,t he acidity of (C 2 F 5 ) 3 GeH was examined by treatment with different bases, for example, 1,8-bis(dimethylamino)naphthalene. The resulting germanate(II)i on [Ge(C 2 F 5 ) 3 ] À serves as ag ermyl group transfer reagent. The reactionw ith main-group and transition-metal complexes or organohalides opens accesst oav ariety of different compounds, the structures of which were mostly determined by X-ray diffraction. The correspondingt ricarbonylnickelate(0) complex [(CO) 3 NiGe(C 2 F 5 ) 3 ] À also gives information about the p-acceptor properties of the [Ge(C 2 F 5 ) 3 ] À ligand.F urthermore, hydrogermylation reactions of (C 2 F 5 ) 3 GeH with alkynes afforded different stereoisomers (a,b-cis, b-trans)d epending on the respective reactionconditions and substrates.