1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling?
✍ Scribed by Rodrigo A. Cormanich; Marilua A. Moreira; Matheus P. Freitas; Teodorico C. Ramalho; Cléber P. A. Anconi; Roberto Rittner; Rubén H. Contreras; Cláudio F. Tormena
- Book ID
- 102951569
- Publisher
- John Wiley and Sons
- Year
- 2011
- Tongue
- English
- Weight
- 578 KB
- Volume
- 49
- Category
- Article
- ISSN
- 0749-1581
- DOI
- 10.1002/mrc.2838
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✦ Synopsis
The present study shows that a hydrogen bond between the OH group and the fluorine atom is not involved in the ^1h^J~FH~ 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 ^1h^J~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 ^nTS^J~FH~ 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 J~FH~ couplings. Copyright © 2011 John Wiley & Sons, Ltd.