Artículos de revistas
1hJFH coupling in 2-fluorophenol revisited: Is intramolecular hydrogen bond responsible for this long-range coupling?
Registro en:
Magnetic Resonance In Chemistry. Wiley-blackwell, v. 49, n. 12, n. 763, n. 767, 2011.
0749-1581
WOS:000298098000001
10.1002/mrc.2838
Autor
Cormanich, RA
Moreira, MA
Freitas, MP
Ramalho, TC
Anconi, CPA
Rittner, R
Contreras, RH
Tormena, CF
Institución
Resumen
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) The present study shows that a hydrogen bond between the OH group and the fluorine atom is not involved in the 1hJFH spinspin 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 1hJFH spinspin 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. Copyright (c) 2011 John Wiley & Sons, Ltd. 49 12 763 767 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) CONICET [PIP 0369/10] UBATEC [X047] Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) CONICET [PIP 0369/10] UBATEC [X047]