On the Nature of Bridging Metal Atoms in Intermetalloid Clusters: Synthesis and Structure of the Metal-Atom-Bridged Zintl Clusters [Sn(Ge9)2]4−and [Zn(Ge9)2)]6−

Manuel M. Bentlohner, Laura Alice Jantke, Thomas Henneberger, Christina Fischer, Kerstin Mayer, Wilhelm Klein, Thomas F. Fässler

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Abstract

The addition of Sn and Zn ions to [Ge9] clusters by reaction of [Ge9]4−with SnPh2Cl2, ZnCp*2(Cp*=pentamethylcyclopentadienyl), or Zn2[HC(Ph2P=NPh)2]2is reported. The resulting Sn- and Zn-bridged clusters [(Ge9)M(Ge9)]q−(M=Sn, q=4; M=Zn, q=6) display various coordination modes. The M atoms that coordinate to the open square of a C4v-symmetric [Ge9] cluster form strong covalent multicenter M−Ge bonds, in contrast to the M atoms coordinating to triangular cluster faces. Molecular orbital analyses show that the M atoms of the Ge9M fragments coordinate to a second [Ge9] cluster with similar orbitals but in different ways. The [Ge9Sn]2−unit donates two electrons to the triangular face of a second [Ge9]2−cluster with D3hsymmetry, whereas [Ge9Zn]2−acts as an electron acceptor when interacting with the triangular face of a D3h-symmetric [Ge9]4−unit.

Original languageEnglish
Pages (from-to)13946-13952
Number of pages7
JournalChemistry - A European Journal
Volume22
Issue number39
DOIs
StatePublished - 19 Sep 2016

Keywords

  • Zintl anions
  • germanium
  • metal–metal interactions
  • tin
  • zinc

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