Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
J Am Chem Soc. 2011 May 4;133(17):6560-2. doi: 10.1021/ja200520c. Epub 2011 Apr 8.
We report a simple and efficient method for replacing germanium atoms in deltahedral Ge(9)(4-) clusters with Sb or Bi. While reactions of Ge(9)(4-) with EPh(3) (E = Sb, Bi) at room temperature are known to produce mono- and disubstituted clusters Ph(2)E-Ge(9)-Ge(9)-EPh(2) and Ph(2)E-Ge(9)-EPh(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 (EGe(8))-(Ge(8)E), (Sb(2)Ge(7))(2-), and (SbGe(8))-SbPh(2).
我们报告了一种简单有效的方法，可将正四面体 Ge(9)(4-) 团簇中的锗原子用 Sb 或 Bi 取代。已知 Ge(9)(4-)与 EPh(3)（E = Sb，Bi）在室温下反应分别生成单取代和双取代的团簇Ph(2)E-Ge(9)-Ge(9)-EPh(2)和Ph(2)E-Ge(9)-EPh(2)，但在高温下或超声处理时，它们会导致 Ge 团簇原子与 Sb 或 Bi 的交换。通过这种反应结构上得到表征的是新型的“n 型掺杂”正四面体形 Zintl 离子(EGe(8))-(Ge(8)E)、(Sb(2)Ge(7))(2-)和(SbGe(8))-SbPh(2)。
