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

J Mol Model. 2013 Jul;19(7):2739-46. doi: 10.1007/s00894-012-1571-4. Epub 2012 Sep 12.

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.

MeSH terms

  • Carbon / chemistry*
  • Computer Simulation
  • Germanium / chemistry
  • Halogens / chemistry*
  • Models, Molecular
  • Nitrogen / chemistry
  • Silicon / chemistry*
  • Static Electricity

Substances

  • Halogens
  • Germanium
  • Carbon
  • Nitrogen
  • Silicon