Will an η3-Si3H3 ligand form sandwich compounds with main group elements?

Academic Article


  • η3-Si3H3 sandwich compounds 5 and 6, with classical and H-bridged ligands, respectively, having the main group elements boron and carbon as central atoms are minima at B3LYP/6-311++G(2d,2p). The stability of these systems is assisted by transfer of charge from the ligands to the central atom and is reversed from that of cyclopentadienyl sandwiches. The C and B containing pyramidal complexes 7, containing both a η3-Si3H3 and a μ2- Si3H3 ligand, are more stable than 5 by 20.7 and 8.5 kcal/mol, respectively. The spiro compounds 8, in which the C and B atoms are sandwiched by two allylic μ2-Si3H3 ligands, are still more stable by 29.6 and 21.9 kcal/mol, respectively. All three types (face-face, face-side, side- side) of sandwich structures are considered viable targets for synthetic pursuit. The Be complexes deviate from the C and B analogues because Be is much more electropositive. In the preferred cluster structure 9 the Be atom sits in a Si6H6 basket.
  • Authors

    Digital Object Identifier (doi)

    Pubmed Id

  • 24745062
  • Author List

  • Srinivas GN; Hamilton TP; Jemmis ED; McKee ML; Lammertsma K
  • Start Page

  • 1725
  • End Page

  • 1728
  • Volume

  • 122
  • Issue

  • 8