Chalcogen and pnicogen bonds in complexes of neutral icosahedral and bicapped square-antiprismatic heteroboranes

J Phys Chem A. 2015 Feb 26;119(8):1388-95. doi: 10.1021/jp511101n. Epub 2015 Feb 12.

Abstract

A systematic quantum mechanical study of σ-hole (chalcogen, pnicogen, and halogen) bonding in neutral experimentally known closo-heteroboranes is performed. Chalcogens and pnicogens are incorporated in the borane cage, whereas halogens are considered as exo-substituents of dicarbaboranes. The chalcogen and pnicogen atoms in the heteroborane cages have partial positive charge and thus more positive σ-holes. Consequently, these heteroboranes form very strong chalcogen and pnicogen bonds. Halogen atoms in dicarbaboranes also have a highly positive σ-hole, but only in the case of C-bonded halogen atoms. In such cases, the halogen bond of heteroboranes is also strong and comparable to halogen bonds in organic compounds with several electron-withdrawing groups being close to the halogen atom involved in the halogen bond.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Boranes / chemistry*
  • Chalcogens / chemistry*
  • Halogens / chemistry
  • Models, Chemical

Substances

  • Boranes
  • Chalcogens
  • Halogens