Do traditional, chlorine-shared, and ion-pair halogen bonds exist? An ab initio investigation of FCl:CNX complexes

J Phys Chem A. 2010 Dec 16;114(49):12958-62. doi: 10.1021/jp110295n. Epub 2010 Nov 16.

Abstract

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to determine the structures, binding energies, and bonding of complexes FCl:CNX, with X = CN, NC, NO(2), F, CF(3), Cl, Br, H, CCF, CCH, CH(3), SiH(3), Li, and Na. Equation-of-motion coupled cluster calculations have also been carried out to determine the coupling constants (1)J(F-Cl), (1X)J(Cl-C), and (2X)J(F-C) across these halogen bonds. As the strength of the base is systematically increased, the nature of the halogen bond changes from traditional, to chlorine-shared, to ion-pair. The type of halogen bond present in a complex can be readily determined from its structure, binding energy, AIM bonding analyses, and spin-spin coupling constants. Coupling constants across halogen bonds are compared with corresponding coupling constants across traditional, proton-shared, and ion-pair hydrogen bonds.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbon / chemistry
  • Cyanides / chemistry
  • Halogens / chemistry*
  • Hydrogen Bonding
  • Ions / chemistry
  • Metals, Alkali / chemistry
  • Nitrogen / chemistry
  • Protons
  • Vibration

Substances

  • Cyanides
  • Halogens
  • Ions
  • Metals, Alkali
  • Protons
  • Carbon
  • Nitrogen