Journal of Molecular Modeling

, Volume 19, Issue 7, pp 2739–2746

Trends in σ-hole strengths and interactions of F3MX molecules (M = C, Si, Ge and X = F, Cl, Br, I)

  • Ashwini Bundhun
  • Ponnadurai Ramasami
  • Jane S. Murray
  • Peter Politzer
Original Paper

DOI: 10.1007/s00894-012-1571-4

Cite this article as:
Bundhun, A., Ramasami, P., Murray, J.S. et al. J Mol Model (2013) 19: 2739. doi:10.1007/s00894-012-1571-4

Abstract

It is well-established that many covalently-bonded atoms of Groups IV–VII have directionally-specific regions of positive electrostatic potential (σ-holes) through which they can interact with negative sites. In the case of Group VII, this is called “halogen bonding.” We have studied two series of molecules: the F3MX and, for comparison, the H3MX (M = C, Si and Ge; X = F, Cl, Br and I). Our objective was to determine how the interplay between M and X in each molecule affects the σ-holes of both, and consequently their interactions with the nitrogen lone pair of HCN. We find that the relative electronegativities of M and X are not sufficient to explain their effects upon each other’s σ-holes; consideration of charge capacity/polarizability (and perhaps other factors) also appears to be necessary. However the results do support the description of normal σ-hole interactions as being largely electrostatically-driven.

Keywords

Halogen bondingElectrostatic potentialsF3MX moleculesInteraction energiesσ-hole interactions

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  • Ashwini Bundhun
    • 1
  • Ponnadurai Ramasami
    • 1
  • Jane S. Murray
    • 2
  • Peter Politzer
    • 2
  1. 1.Computational Chemistry Group, Department of ChemistryUniversity of MauritiusReduitMauritius
  2. 2.CleveTheoCompClevelandUSA