jp511101n_si_001.pdf (309.73 kB)
Chalcogen and Pnicogen Bonds in Complexes of Neutral Icosahedral and Bicapped Square-Antiprismatic Heteroboranes
journal contribution
posted on 2015-02-26, 00:00 authored by Adam Pecina, Martin Lepšík, Drahomír Hnyk, Pavel Hobza, Jindřich FanfrlíkA 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.