How to twist, split and warp a σ‑Hole with hypervalent halogens

Omer Kirshenboim, Sebastian Kozuch

Research output: Contribution to journalArticlepeer-review

34 Scopus citations

Abstract

Halogen bonds (XB) are no longer newcomers in the chemistry family. However, XB in hypervalent halogens has not been thoroughly studied. We provide a molecular orbital explanation of the shape and strength of XBs in hypervalent halogens and other species, focusing on the charge transfer and electrostatic aspects of these bonds. Our results show that σ-holes (and subsequently the XBs associated with them) can be easily divided and bent by the influence of equatorial substituents. The inductive effect of both the equatorial and axial groups can affect these distortions, but also the angle between the equatorial ligands has a large influence on the shape of the σ-holes and the molecular orbitals acting as electron acceptor. Although the observation of these warped XB can be hindered by other noncovalent interactions, they May be ubiquitous in crystal structures of hypervalent species, where multiple XB can appear as secondary interactions on each halogen. We propose what can be considered the archetypal hypervalent halogen donor (a pincer type iodosodilactone) and a Lewis dot structure that includes the σ-holes.

Original languageEnglish
Pages (from-to)9431-9445
Number of pages15
JournalJournal of Physical Chemistry A
Volume120
Issue number47
DOIs
StatePublished - 1 Dec 2016

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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