NMR parameters and geometries of OHN and ODN hydrogen bonds of pyridine-acid complexes

Chemistry. 2004 Oct 11;10(20):5195-204. doi: 10.1002/chem.200400212.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acids / chemistry*
  • Deuterium / chemistry*
  • Hydrogen / chemistry*
  • Hydrogen Bonding
  • Magnetic Resonance Spectroscopy
  • Molecular Structure
  • Nitrogen / chemistry*
  • Oxygen / chemistry*
  • Pyridines / chemistry*
  • Vibration

Substances

  • Acids
  • Pyridines
  • Hydrogen
  • Deuterium
  • Nitrogen
  • pyridine
  • Oxygen