Subvalent mixed SixGey oligomers: (Cl3Si)4Ge and Cl2(Me2EtN)SiGe(SiCl3)2

(Cl3Si)4Ge (1; 91%) is accessible from GeCl4, the Si2Cl6/[nBu4N]Cl silylation system, and excess SiCl4. A key intermediate step involves Cl− sequestration with AlCl3 in the course of the reaction between the first-formed germanide [(Cl3Si)3Ge]− and SiCl4. The related adduct Cl2(Me2EtN)SiGe(SiCl3)2 (2; quantitative conversion) was prepared either by amine-induced cleavage of 1 or by a bottom-up synthesis starting from GeCl4 and Si2Cl6.