DOI

In this paper, equations are proposed which relate various NMR parameters of OHN hydrogen-bonded pyridine-acid complexes to their bond valences which are in turn correlated with their hydrogen-bond geometries. As the valence bond model is strictly valid only for weak hydrogen bonds appropriate empirical correction factors are proposed which take into account anharmonic zero-point energy vibrations. The correction factors are different for OHN and ODN hydrogen bonds and depend on whether a double or a single well potential is realized in the strong hydrogen-bond regime. One correction factor was determined from the known experimental structure of a very strong OHN hydrogen bond between pentachlorophenol and 4-methylpyridine, determined by the neutron diffraction method. The remaining correction factors which allow one also to describe H/D isotope effects on the NMR parameters and geometries of OHN hydrogen bond were determined by analysing the NMR parameters of the series of protonated and deuterated pyridine- and collidine-acid complexes. The method may be used in the future to establish hydrogen-bond geometries in biologically relevant functional OHN hydrogen bonds.

Original languageEnglish
Pages (from-to)5195-5204
Number of pages10
JournalChemistry - A European Journal
Volume10
Issue number20
DOIs
StatePublished - 11 Oct 2004

    Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

    Research areas

  • Acid-base complexes, Hydrogen bonds, Isotope effects, NMR parameters

ID: 43112731