Jump to main content
Jump to site search

Issue 7, 2015
Previous Article Next Article

Counterion influence on the N–I–N halogen bond

Author affiliations

Abstract

A detailed investigation of the influence of counterions on the [N–I–N]+ halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N–I–N]+ halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in the solid state by single crystal X-ray crystallography. Molecular systems encompassing weakly coordinating counterions behave similarly to the corresponding silver(I) centered coordination complexes. In contrast, systems possessing moderately or strongly coordinating anions show a distinctly different behavior. Such silver(I) complexes are converted into multi-coordinate geometries with strong Ag–O bonds, whereas the iodine centered systems remain linear and lack direct charge transfer interaction with the counterion, as verified by 15N NMR and DFT computation. This suggests that the [N–I–N]+ halogen bond may not be satisfactorily described in terms of a pure coordination bond typical of transition metal complexes, but as a secondary bond with a substantial charge-transfer character.

Graphical abstract: Counterion influence on the N–I–N halogen bond

Back to tab navigation

Supplementary files

Publication details

The article was received on 23 Mar 2015, accepted on 20 Apr 2015 and first published on 20 Apr 2015


Article type: Edge Article
DOI: 10.1039/C5SC01053E
Author version
available:
Download author version (PDF)
Citation: Chem. Sci., 2015,6, 3746-3756
  • Open access: Creative Commons BY license
  •   Request permissions

    Counterion influence on the N–I–N halogen bond

    M. Bedin, A. Karim, M. Reitti, A. C. Carlsson, F. Topić, M. Cetina, F. Pan, V. Havel, F. Al-Ameri, V. Sindelar, K. Rissanen, J. Gräfenstein and M. Erdélyi, Chem. Sci., 2015, 6, 3746
    DOI: 10.1039/C5SC01053E

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements