Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19F NMR Shifts versus Thermochemistry
Abstract A comparison of computed 19F NMR chemical shifts and experiment provides evidence for large specific solvent effects for fluoride‐type anions interacting with the σ*(C−H) orbitals in organic solvents like MeCN or CH2Cl2. We show this for systems ranging from the fluoride ion and the bifluor...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2022-12-01
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| Series: | ChemistryOpen |
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| Online Access: | https://doi.org/10.1002/open.202200146 |
| _version_ | 1797954165687713792 |
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| author | Prof. Dr. Martin Kaupp Caspar J. Schattenberg Dr. Robert Müller Marc Reimann |
| author_facet | Prof. Dr. Martin Kaupp Caspar J. Schattenberg Dr. Robert Müller Marc Reimann |
| author_sort | Prof. Dr. Martin Kaupp |
| collection | DOAJ |
| description | Abstract A comparison of computed 19F NMR chemical shifts and experiment provides evidence for large specific solvent effects for fluoride‐type anions interacting with the σ*(C−H) orbitals in organic solvents like MeCN or CH2Cl2. We show this for systems ranging from the fluoride ion and the bifluoride ion [FHF]− to polyhalogen anions [ClFx]−. Discrepancies between computed and experimental shifts when using continuum solvent models like COSMO or force‐field‐based descriptions like the 3D‐RISM‐SCF model show specific orbital interactions that require a quantum‐mechanical treatment of the solvent molecules. This is confirmed by orbital analyses of the shielding constants, while less negatively charged fluorine atoms (e. g., in [EF4]−) do not require such quantum‐mechanical treatments to achieve reasonable accuracy. The larger 19F solvent shift of fluoride in MeCN compared to water is due to the larger coordination number in the former. These observations are due to unusually strong charge‐assisted C−H⋅⋅⋅F− hydrogen bonds, which manifest beyond some threshold negative natural charge on fluorine of ca. < −0.6 e. The interactions are accompanied by sizable free energies of solvation, in the order F−≫[FHF]−>[ClF2]−>[ClF4]−. COSMO‐RS solvation free energies tend to moderately underestimate those from the micro‐solvated cluster treatment. Red‐shifted and intense vibrational C−H stretching bands, potentially accessible in bulk solution, are further spectroscopic finger prints. |
| first_indexed | 2024-04-10T23:14:22Z |
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| id | doaj.art-606d2fec71804ed583d6eb2c0c00430c |
| institution | Directory Open Access Journal |
| issn | 2191-1363 |
| language | English |
| last_indexed | 2024-04-10T23:14:22Z |
| publishDate | 2022-12-01 |
| publisher | Wiley-VCH |
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| series | ChemistryOpen |
| spelling | doaj.art-606d2fec71804ed583d6eb2c0c00430c2023-01-13T01:50:53ZengWiley-VCHChemistryOpen2191-13632022-12-011112n/an/a10.1002/open.202200146Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19F NMR Shifts versus ThermochemistryProf. Dr. Martin Kaupp0Caspar J. Schattenberg1Dr. Robert Müller2Marc Reimann3Technische Universität Berlin Institut für Chemie, Theoretische Chemie/Quantenchemie Sekr. C7, Strasse des 17. Juni 135 10623 Berlin GermanyTechnische Universität Berlin Institut für Chemie, Theoretische Chemie/Quantenchemie Sekr. C7, Strasse des 17. Juni 135 10623 Berlin GermanyTechnische Universität Berlin Institut für Chemie, Theoretische Chemie/Quantenchemie Sekr. C7, Strasse des 17. Juni 135 10623 Berlin GermanyTechnische Universität Berlin Institut für Chemie, Theoretische Chemie/Quantenchemie Sekr. C7, Strasse des 17. Juni 135 10623 Berlin GermanyAbstract A comparison of computed 19F NMR chemical shifts and experiment provides evidence for large specific solvent effects for fluoride‐type anions interacting with the σ*(C−H) orbitals in organic solvents like MeCN or CH2Cl2. We show this for systems ranging from the fluoride ion and the bifluoride ion [FHF]− to polyhalogen anions [ClFx]−. Discrepancies between computed and experimental shifts when using continuum solvent models like COSMO or force‐field‐based descriptions like the 3D‐RISM‐SCF model show specific orbital interactions that require a quantum‐mechanical treatment of the solvent molecules. This is confirmed by orbital analyses of the shielding constants, while less negatively charged fluorine atoms (e. g., in [EF4]−) do not require such quantum‐mechanical treatments to achieve reasonable accuracy. The larger 19F solvent shift of fluoride in MeCN compared to water is due to the larger coordination number in the former. These observations are due to unusually strong charge‐assisted C−H⋅⋅⋅F− hydrogen bonds, which manifest beyond some threshold negative natural charge on fluorine of ca. < −0.6 e. The interactions are accompanied by sizable free energies of solvation, in the order F−≫[FHF]−>[ClF2]−>[ClF4]−. COSMO‐RS solvation free energies tend to moderately underestimate those from the micro‐solvated cluster treatment. Red‐shifted and intense vibrational C−H stretching bands, potentially accessible in bulk solution, are further spectroscopic finger prints.https://doi.org/10.1002/open.202200146NMR chemical shiftssolvation effectshydrogen bondingdensity functional theorysolvation free energy |
| spellingShingle | Prof. Dr. Martin Kaupp Caspar J. Schattenberg Dr. Robert Müller Marc Reimann Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19F NMR Shifts versus Thermochemistry ChemistryOpen NMR chemical shifts solvation effects hydrogen bonding density functional theory solvation free energy |
| title | Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19F NMR Shifts versus Thermochemistry |
| title_full | Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19F NMR Shifts versus Thermochemistry |
| title_fullStr | Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19F NMR Shifts versus Thermochemistry |
| title_full_unstemmed | Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19F NMR Shifts versus Thermochemistry |
| title_short | Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19F NMR Shifts versus Thermochemistry |
| title_sort | unusually large effects of charge assisted c h⋅⋅⋅f hydrogen bonds to anionic fluorine in organic solvents computational study of 19f nmr shifts versus thermochemistry |
| topic | NMR chemical shifts solvation effects hydrogen bonding density functional theory solvation free energy |
| url | https://doi.org/10.1002/open.202200146 |
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