Robertson, C.C., Perutz, R.N., Brammer, L. orcid.org/0000-0001-6435-7197 et al. (1 more author) (2014) A solvent-resistant halogen bond. Chemical Science, 5 (11). pp. 4179-4183. ISSN 2041-6520
Abstract
The effect of solvent on the stabilities of complexes involving a single H-bond or halogen-bond (X-bond) has been quantified. Association constants for binary complexes of 4-(phenylazo)phenol, molecular iodine, tetramethylurea and tetramethylthiourea have been measured in fifteen different solvents by UV/vis absorption and 1H NMR titration experiments. The stabilities of the H-bonded complexes decrease by more than three orders of magnitude with increasing solvent polarity. In contrast, the X-bonded complex of molecular iodine with tetramethylthiourea is remarkably insensitive to the nature of the solvent (association constants measured in alkanes and alcohols are similar). The results suggest that, in contrast to H-bonds, where electrostatics determine thermodynamic stability, charge-transfer interactions make a major contribution to the stability of these X-bonded complexes rendering them resistant to increases in solvent polarity.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2014 The Royal Society of Chemistry. This is an Open Access article distributed under the terms of the Creative Commons Attribution Licence (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 27 Oct 2016 14:05 |
Last Modified: | 27 Oct 2016 14:05 |
Published Version: | https://dx.doi.org/10.1039/C4SC01746C |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Refereed: | Yes |
Identification Number: | 10.1039/C4SC01746C |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:106350 |