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Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction

An investigation of C–F⋯H–O hydrogen bonds in the complexes CH(n)XCH(n)F⋯H(2)O (n = 0, 1, 2; X = H, F, Cl, Br) was performed at the MP2/aug-cc-pVTZ level. We found that the electron-withdrawing halogen substituents on the vicinal carbon cause the fluorine atom, participating in the hydrogen bond for...

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Autores principales: Jia, Qingqing, Li, Qingzhong, Luo, Mo, Li, Hai-Bei
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9090643/
https://www.ncbi.nlm.nih.gov/pubmed/35558337
http://dx.doi.org/10.1039/c8ra08122k
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author Jia, Qingqing
Li, Qingzhong
Luo, Mo
Li, Hai-Bei
author_facet Jia, Qingqing
Li, Qingzhong
Luo, Mo
Li, Hai-Bei
author_sort Jia, Qingqing
collection PubMed
description An investigation of C–F⋯H–O hydrogen bonds in the complexes CH(n)XCH(n)F⋯H(2)O (n = 0, 1, 2; X = H, F, Cl, Br) was performed at the MP2/aug-cc-pVTZ level. We found that the electron-withdrawing halogen substituents on the vicinal carbon cause the fluorine atom, participating in the hydrogen bond formation, to be less negatively charged. Thus, the halogen groups weaken the strength of organofluorine hydrogen bond by inductive effect. The position of the substituents on the vicinal carbon affects the strength of the C–F⋯H–O interaction. Compared with that in other isomers, the electron withdrawing substituent in 1-fluoro-ethane with stagger conformation as well as in 1-fluoro-ethene with trans configuration much weakens the interaction of C–F⋯H–O due to the hyperconjugative interaction between σ((C–F)) and [Image: see text]. By analogy, the electron-donating ones could largely strengthen it. We found that there is a good linear relationship between electron density at the BCP of F⋯H and Wiberg bond indexes (WBI) as well as between natural bond-bond polarizability (NBBP) and WBI, which indicates that the magnitude of NBBP and WBI could be a good indicator of the hydrogen bond strength.
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spelling pubmed-90906432022-05-11 Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction Jia, Qingqing Li, Qingzhong Luo, Mo Li, Hai-Bei RSC Adv Chemistry An investigation of C–F⋯H–O hydrogen bonds in the complexes CH(n)XCH(n)F⋯H(2)O (n = 0, 1, 2; X = H, F, Cl, Br) was performed at the MP2/aug-cc-pVTZ level. We found that the electron-withdrawing halogen substituents on the vicinal carbon cause the fluorine atom, participating in the hydrogen bond formation, to be less negatively charged. Thus, the halogen groups weaken the strength of organofluorine hydrogen bond by inductive effect. The position of the substituents on the vicinal carbon affects the strength of the C–F⋯H–O interaction. Compared with that in other isomers, the electron withdrawing substituent in 1-fluoro-ethane with stagger conformation as well as in 1-fluoro-ethene with trans configuration much weakens the interaction of C–F⋯H–O due to the hyperconjugative interaction between σ((C–F)) and [Image: see text]. By analogy, the electron-donating ones could largely strengthen it. We found that there is a good linear relationship between electron density at the BCP of F⋯H and Wiberg bond indexes (WBI) as well as between natural bond-bond polarizability (NBBP) and WBI, which indicates that the magnitude of NBBP and WBI could be a good indicator of the hydrogen bond strength. The Royal Society of Chemistry 2018-11-20 /pmc/articles/PMC9090643/ /pubmed/35558337 http://dx.doi.org/10.1039/c8ra08122k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Jia, Qingqing
Li, Qingzhong
Luo, Mo
Li, Hai-Bei
Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction
title Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction
title_full Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction
title_fullStr Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction
title_full_unstemmed Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction
title_short Understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction
title_sort understanding the effects of vicinal carbon substituents and configuration on organofluorine hydrogen-bonding interaction
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9090643/
https://www.ncbi.nlm.nih.gov/pubmed/35558337
http://dx.doi.org/10.1039/c8ra08122k
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