The Antagonist Effect of Nitrogen Lone Pair: 3JHF versus 5JHF

Thaís M. Barbosa, Renan V. Viesser, Lucas G. Martins, Roberto Rittner, Cláudio F. Tormena

Resultado de la investigación: Contribución a una revistaArtículo (Contribución a Revista)revisión exhaustiva

3 Citas (Scopus)

Resumen

The long-range scalar coupling constant between proton and fluorine nuclei, 5JHF, is observed to be larger than 3JHF in the pyrimidinyl moiety of voriconazole. A set of smaller molecules is chosen (fluorobenzene, N-methyl-2-fluoropyridine, N-methyl-3-fluoropyridine, 3-fluoropyridine, 5-pyrimidine, and 2-fluoropyridine) to evaluate the influence of the nitrogen atom in the experimental JHF values. Spectral aliased pure shift heteronuclear single quantum coherence spectroscopy (SAPS-HSQC) is applied to determine the relative sign between the JCF and JHF scalar couplings. Theoretical calculations show that the 3JHF and 5JHF coupling constants can be described mainly by a Fermi contact (FC) transmission mechanism. A decomposition analysis of JHF in terms of localized molecular orbital (LMO) contributions allows us to determine that the interaction involving the nitrogen lone pair (LPN) is the main reason for the larger 5JHF compared to 3JHF. Our analysis indicates that delocalization of LPN has a positive contribution to the long-range coupling, while a negative one is observed for 3JHF.

Idioma originalInglés
Páginas (desde-hasta)1358-1362
Número de páginas5
PublicaciónChemPhysChem
Volumen19
N.º11
DOI
EstadoPublicada - 5 jun 2018
Publicado de forma externa

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