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

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

Research output: Contribution to journalArticle (Contribution to Journal)peer-review

4 Scopus citations


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.

Original languageEnglish
Pages (from-to)1358-1362
Number of pages5
Issue number11
StatePublished - 5 Jun 2018
Externally publishedYes


  • coupling constants
  • fluorinated compounds
  • NMR
  • orbital decomposition analysis
  • pyrimidinyl moiety


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