1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling?
The present study shows that a hydrogen bond between the OH group and the fluorine atom is not involved in the 1hJFH spin-spin coupling transmission either for 4-bromo-2-fluorophenol or 2-fluorophenol. In fact, according to a quantum theory of atoms in molecules analysis, no bond critical point is f...
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todo:paper_07491581_v49_n12_p763_Cormanich2023-10-03T15:39:32Z 1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling? Cormanich, R.A. Moreira, M.A. Freitas, M.P. Ramalho, T.C. Anconi, C.P.A. Rittner, R. Contreras, R.H. Tormena, C.F. 2-fluorophenol coupling constant FCCP-CMO intramolecular H-bonding QTAIM 2 fluorophenol 2-fluorophenol acetonitrile acetonitrile derivative cyclohexane cyclohexane derivative phenol derivative article chemical structure chemistry electron hydrogen bond methodology nuclear magnetic resonance spectroscopy physical chemistry quantum theory thermodynamics Acetonitriles Chemistry, Physical Cyclohexanes Electrons Hydrogen Bonding Magnetic Resonance Spectroscopy Models, Molecular Phenols Quantum Theory Thermodynamics The present study shows that a hydrogen bond between the OH group and the fluorine atom is not involved in the 1hJFH spin-spin coupling transmission either for 4-bromo-2-fluorophenol or 2-fluorophenol. In fact, according to a quantum theory of atoms in molecules analysis, no bond critical point is found between O-H and F moieties. The nature of the transmission mechanism of the Fermi contact term of the 1hJ FH spin-spin coupling is studied by analyzing canonical molecular orbitals (see J. Phys. Chem. A 2010, 114, 1044), and it is observed that virtual orbitals play only a quite minor role in its transmission. This is typical of a Fermi contact term transmitted mainly through exchange interactions owing to the overlap of proximate electronic clouds; therefore, it is suggested to identify them as nTSJFH coupling where n stands for the number of formal bonds separating the coupling nuclei. In the cases studied in this work is n = 4. Results presented in this work could provide an interesting rationalization for different experimental signs known in the current literature for proximate JFH couplings. © 2011 John Wiley & Sons, Ltd. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_07491581_v49_n12_p763_Cormanich |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
2-fluorophenol coupling constant FCCP-CMO intramolecular H-bonding QTAIM 2 fluorophenol 2-fluorophenol acetonitrile acetonitrile derivative cyclohexane cyclohexane derivative phenol derivative article chemical structure chemistry electron hydrogen bond methodology nuclear magnetic resonance spectroscopy physical chemistry quantum theory thermodynamics Acetonitriles Chemistry, Physical Cyclohexanes Electrons Hydrogen Bonding Magnetic Resonance Spectroscopy Models, Molecular Phenols Quantum Theory Thermodynamics |
| spellingShingle |
2-fluorophenol coupling constant FCCP-CMO intramolecular H-bonding QTAIM 2 fluorophenol 2-fluorophenol acetonitrile acetonitrile derivative cyclohexane cyclohexane derivative phenol derivative article chemical structure chemistry electron hydrogen bond methodology nuclear magnetic resonance spectroscopy physical chemistry quantum theory thermodynamics Acetonitriles Chemistry, Physical Cyclohexanes Electrons Hydrogen Bonding Magnetic Resonance Spectroscopy Models, Molecular Phenols Quantum Theory Thermodynamics Cormanich, R.A. Moreira, M.A. Freitas, M.P. Ramalho, T.C. Anconi, C.P.A. Rittner, R. Contreras, R.H. Tormena, C.F. 1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling? |
| topic_facet |
2-fluorophenol coupling constant FCCP-CMO intramolecular H-bonding QTAIM 2 fluorophenol 2-fluorophenol acetonitrile acetonitrile derivative cyclohexane cyclohexane derivative phenol derivative article chemical structure chemistry electron hydrogen bond methodology nuclear magnetic resonance spectroscopy physical chemistry quantum theory thermodynamics Acetonitriles Chemistry, Physical Cyclohexanes Electrons Hydrogen Bonding Magnetic Resonance Spectroscopy Models, Molecular Phenols Quantum Theory Thermodynamics |
| description |
The present study shows that a hydrogen bond between the OH group and the fluorine atom is not involved in the 1hJFH spin-spin coupling transmission either for 4-bromo-2-fluorophenol or 2-fluorophenol. In fact, according to a quantum theory of atoms in molecules analysis, no bond critical point is found between O-H and F moieties. The nature of the transmission mechanism of the Fermi contact term of the 1hJ FH spin-spin coupling is studied by analyzing canonical molecular orbitals (see J. Phys. Chem. A 2010, 114, 1044), and it is observed that virtual orbitals play only a quite minor role in its transmission. This is typical of a Fermi contact term transmitted mainly through exchange interactions owing to the overlap of proximate electronic clouds; therefore, it is suggested to identify them as nTSJFH coupling where n stands for the number of formal bonds separating the coupling nuclei. In the cases studied in this work is n = 4. Results presented in this work could provide an interesting rationalization for different experimental signs known in the current literature for proximate JFH couplings. © 2011 John Wiley & Sons, Ltd. |
| format |
JOUR |
| author |
Cormanich, R.A. Moreira, M.A. Freitas, M.P. Ramalho, T.C. Anconi, C.P.A. Rittner, R. Contreras, R.H. Tormena, C.F. |
| author_facet |
Cormanich, R.A. Moreira, M.A. Freitas, M.P. Ramalho, T.C. Anconi, C.P.A. Rittner, R. Contreras, R.H. Tormena, C.F. |
| author_sort |
Cormanich, R.A. |
| title |
1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling? |
| title_short |
1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling? |
| title_full |
1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling? |
| title_fullStr |
1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling? |
| title_full_unstemmed |
1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling? |
| title_sort |
1hjfh coupling in 2-fluorophenol revisited: is intramolecular hydrogen bond responsible for this long-range coupling? |
| url |
http://hdl.handle.net/20.500.12110/paper_07491581_v49_n12_p763_Cormanich |
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