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. ...
PublisherR S C Publications
Publication in research information system
MetadataShow full item record
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.
Showing items with similar title or keywords.
Influence of substituents in aromatic ring on the strength of halogen bonding in iodobenzene derivatives Chernysheva, Maria V.; Bulatova, Margarita; Ding, Xin; Haukka, Matti (American Chemical Society (ACS), 2020)Halogen bonding properties of 3,4,5-triiodobenzoic acid (1, 2), 1,2,3-triiodobenzene (3), pentaiodobenzoic acid ethanol solvate (4), hexaiodobenzene (5a, 5b, 5c), 2,4-diiodoaniline (6), 4-iodoaniline (7), 2-iodoaniline ...
Halogen bond in crystal engineering : structural studies on crystals with neutral ruthenium centered complexes and 1-(4-pyridyl)-4-thiopyridine zwitterion as halogen bond acceptors Ding, Xin (2020)This work focuses on using both ruthenium complexes and a newly synthesized organic zwitterion as halogen bond (XB) acceptors to construct a series of crystal structures and to investigate the selectivity of halogen bond. ...
Halogen-Bonded Co-Crystals of Aromatic N-oxides : Polydentate Acceptors for Halogen and Hydrogen Bonds Puttreddy, Rakesh; Topic, Filip; Valkonen, Arto; Rissanen, Kari (MDPI AG, 2017)The C-ethyl-2-methylresorcinarene (1) forms 1:1 in-cavity complexes with aromatic N,N′-dioxides, only if each of the aromatic rings has an N−O group. The structurally different C-shaped 2,2′-bipyridine N,N′-dioxide ...
Bamboo-like Chained Cavities and Other Halogen-Bonded Complexes from Tetrahaloethynyl Cavitands with Simple Ditopic Halogen Bond Acceptors Turunen, Lotta; Pan, FangFang; Beyeh, Ngong Kodiah; Trant, John F.; Ras, Robin H. A.; Rissanen, Kari (American Chemical Society, 2018)Halogen bonding provides a useful complement to hydrogen bonding and metal-coordination as a tool for organizing supramolecular systems. Resorcinarenes, tetrameric bowl-shaped cavitands, have been previously shown to ...
Kääpä, Laura (2021)Sosiaalisessa mediassa toimivien vaikuttajien määrä on lisääntynyt huomattavasti viime vuosina. Organisaatiot pyrkivät luomaan näiden sosiaalisen median vaikuttajien kanssa samaistuttavia sisältöjä, joiden avulla tavoitellaan ...