Trichlorosilylated tetrelides [(Cl3Si)3E]− have been prepared by adding 1 equiv of a soluble Cl− salt to (Cl3Si)4Si (E=Si) or 4 Si2Cl6/GeCl4 (E=Ge). To assess their donor qualities, the anions [(Cl3Si)3E]− (E=C, Si, Ge) have been treated with BCl3, AlCl3, and GaCl3. Both BCl3 and GaCl3 give 1:1 adducts with the anionic centers. AlCl3 leads to Cl− abstraction from [(Cl3Si)3E]− with formation of (Cl3Si)4E (E=Si or Ge). (Cl3Si)4Ge is cleanly converted to the perhydrogenated (H3Si)4Ge by use of Li[AlH4]. Another case of Cl− abstraction was observed for [(Cl3Si)3Ge⋅GaCl3]−, which reacts with GaCl3 to afford the neutral dimer [(Cl3Si)3Ge−GaCl2]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...