Why is the antipodal effect in closo-1-SB9H9 so large? A possible explanation based on the geometry from the concerted use of gas electron diffraction and computational methods

Drahomir Hnyk, Derek A. Wann, Josef Holub, Svein Samdal, David W. H. Rankin

Research output: Contribution to journalArticlepeer-review

Abstract

The molecular structure of 1-thia-closo-decaborane(9), 1-SB9H9, has been determined by the concerted use of gas electron diffraction and quantum-chemical calculations. Assuming C4v symmetry, the cage structure was distorted from a symmetrically bicapped square antiprism (D4d symmetry) mainly through substantial expansion of the tetragonal belt of boron atoms adjacent to sulfur. The S-B and (B-B)mean distances are well determined with rh1 = 193.86(14) and 182.14(8) pm, respectively. Geometrical parameters calculated using the MP2(full)/6-311++G** method and at levels reported earlier [MP2(full)/6-311G**, B3LYP/6-311G** and B3LYP/cc-pVQZ], as well as calculated vibrational amplitudes and 11B NMR chemical shifts, are in good agreement with the experimental findings. In particular, the so-called antipodal chemical shift of apical B(10) (71.8 ppm) is reproduced well by the GIAO-MP2 calculations and its large magnitude is schematically accounted for, as is the analogous antipodal chemical shift of B(12) in the twelve-vertex closo-1-SB11H11.

Original languageEnglish
Pages (from-to)5734-5737
Number of pages4
JournalDalton Transactions
Volume40
Issue number21
DOIs
Publication statusPublished - 2011

Keywords

  • CHEMICAL-SHIFT CALCULATIONS
  • AB-INITIO CALCULATIONS
  • MOLECULAR-STRUCTURE
  • CRYSTALLINE PHASES
  • HETEROBORANES
  • BORANES
  • AROMATICITY
  • 1-SB9H9

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