“n-Doping” of Deltahedral Zintl Ions

We report a simple and efficient method for replacing germanium atoms in deltahedral Ge94− clusters with Sb or Bi. While reactions of Ge94− with EPh3 (E = Sb, Bi) at room temperature are known to produce mono- and disubstituted clusters [Ph2E-Ge9-Ge9-EPh2]4− and [Ph2E-Ge9-EPh2]2−, respectively, at elevated temperatures or with sonication they result in exchange of Ge cluster atoms with Sb or Bi. Structurally characterized from such reactions are the novel “n-doped” deltahedral Zintl ions [(EGe8)-(Ge8E)]4−, (Sb2Ge7)2−, and [(SbGe8)-SbPh2]2−.