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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; (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 10.1039/d2cp02317b. (In press). Green open access

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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.

Type: Article
Title: A computational tool to accurately and quickly predict ¹⁹F NMR chemical shifts of molecules with fluorine–carbon and fluorine–boron bonds
Open access status: An open access version is available from UCL Discovery
DOI: 10.1039/d2cp02317b
Publisher version: https://doi.org/10.1039/d2cp02317b
Language: English
Additional information: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/).
UCL classification: UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL
URI: https://discovery.ucl.ac.uk/id/eprint/10154264
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