Alexandre S. Dumon
A computational tool to accurately and quickly predict 19F NMR chemical shifts of molecules with fluorine–carbon and fluorine–boron bonds
Dumon, Alexandre S.; Rzepa, Henry S.; Alamillo-Ferrer, Carla; Bures, Jordi; Procter, Richard; Sheppard, Tom D.; Whiting, Andrew
Authors
Henry S. Rzepa
Carla Alamillo-Ferrer
Jordi Bures
Richard Procter
Tom D. Sheppard
Andrew Whiting andy.whiting@durham.ac.uk
Emeritus Professor
Abstract
We report the evaluation of density-functional-theory (DFT) based procedures for predicting 19F NMR chemical shifts at modest computational cost for a range of molecules with fluorine bonds, to be used as a tool for assisting the characterisation of reaction intermediates and products and as an aid to identifying mechanistic pathways. The results for a balanced learning set of molecules were then checked using two further testing sets, resulting in the recommendation of the ωB97XD/aug-cc-pvdz DFT method and basis set as having the best combination of accuracy and computational time, with a RMS error of 3.57 ppm. Cationic molecules calculated without counter-anion showed normal errors, whilst anionic molecules showed somewhat larger errors. The method was applied to the prediction of the conformationally averaged 19F chemical shifts of 2,2,3,3,4,4,5,5-octafluoropentan-1-ol, in which gauche stereoelectronic effects involving fluorine dominate and to determining the position of coordination equilibria of fluorinated boranes as an aid to verifying the relative energies of intermediate species involved in catalytic amidation reactions involving boron catalysts.
Citation
Dumon, A. S., Rzepa, H. S., Alamillo-Ferrer, C., Bures, J., Procter, R., Sheppard, T. D., & Whiting, A. (2022). A computational tool to accurately and quickly predict 19F NMR chemical shifts of molecules with fluorine–carbon and fluorine–boron bonds. Physical Chemistry Chemical Physics, 24(34), 20409 - 20425. https://doi.org/10.1039/d2cp02317b
Journal Article Type | Article |
---|---|
Acceptance Date | Aug 8, 2022 |
Online Publication Date | Aug 9, 2022 |
Publication Date | 2022 |
Deposit Date | Sep 15, 2022 |
Publicly Available Date | Sep 15, 2022 |
Journal | Physical Chemistry Chemical Physics |
Print ISSN | 1463-9076 |
Electronic ISSN | 1463-9084 |
Publisher | Royal Society of Chemistry |
Peer Reviewed | Peer Reviewed |
Volume | 24 |
Issue | 34 |
Pages | 20409 - 20425 |
DOI | https://doi.org/10.1039/d2cp02317b |
Public URL | https://durham-repository.worktribe.com/output/1191679 |
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Publisher Licence URL
http://creativecommons.org/licenses/by/3.0/
Copyright Statement
Advance online version This work is licensed under a Creative Commons Attribution 3.0 Unported License.
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