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Counterion influence on the N-I-N halogen bond

Journal article
Authors Michele Bedin
Alavi Karim
Marcus Reitti
Anna-Carin Carlsson
Filip Topic
M Cetina
Fanfang Pan
V. Havel
Fatima Al-Ameri
Vladimir Sindelar
Kari Rissanen
Jürgen Gräfenstein
Mate Erdelyi
Published in Chemical Science
Volume 6
Issue 7
Pages 3746-3756
Publication year 2015
Published at Swedish NMR Centre at Göteborg University
Department of Chemistry and Molecular Biology
Pages 3746-3756
Language en
Keywords halogen bond, NMR, counterion, chemical bond
Subject categories Spectroscopy, Organic Chemistry, Organic synthesis, Physical organic chemistry


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.

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