10.1021/jp511101n.s001 Adam Pecina Adam Pecina Martin Lepšík Martin Lepšík Drahomír Hnyk Drahomír Hnyk Pavel Hobza Pavel Hobza Jindřich Fanfrlík Jindřich Fanfrlík Chalcogen and Pnicogen Bonds in Complexes of Neutral Icosahedral and Bicapped Square-Antiprismatic Heteroboranes American Chemical Society 2015 pnicogen heteroborane chalcogen halogen bond 2015-02-26 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Chalcogen_and_Pnicogen_Bonds_in_Complexes_of_Neutral_Icosahedral_and_Bicapped_Square_Antiprismatic_Heteroboranes/2192200 A systematic quantum mechanical study of σ-hole (chalcogen, pnicogen, and halogen) bonding in neutral experimentally known <i>closo</i>-heteroboranes is performed. Chalcogens and pnicogens are incorporated in the borane cage, whereas halogens are considered as <i>exo</i>-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.