Counterion influence on the N–I–N halogen bond
Bedin, M., Karim, A., Reitti, M., Carlsson, A.-C. C., Topic, F., Cetina, M., Pan, F., Havel, V., Al-Ameri, F., Sindelar, V., Rissanen, K., Gräfenstein, J., & Erdély, M. (2015). Counterion influence on the N–I–N halogen bond. Chemical Science, 6(7), 3746-3756. https://doi.org/10.1039/C5SC01053E
Published inChemical Science
© 2015 The Authors. Published by The Royal Society of Chemistry. This is an Open Access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work in properly cited. The Creative Commons Public Domain Dedication waiver applies to the data made available in this article, unless otherwise stated.
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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Except where otherwise noted, this item's license is described as © 2015 The Authors. Published by The Royal Society of Chemistry. This is an Open Access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work in properly cited. The Creative Commons Public Domain Dedication waiver applies to the data made available in this article, unless otherwise stated.
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