ABSTRACT
I. Introduction ...................................................................................................................... 193
II. Theoretical Section .......................................................................................................... 194
A. The Crystallographic View of Hydrogen Bonded Systems .................................... 194
B. Origin of Hydrogen Bond Isotope Effects............................................................... 196
1. Influence of the Hydron Potential..................................................................... 196
2. Effects of the Environment ............................................................................... 197
C. Inclusion of Quantum Corrections in Hydrogen Bond Correlations ...................... 198
D. H/D Isotope Effects on NMR Parameters and Hydrogen Bond
Geometries: The Point Approximation.................................................................... 202
E. H/D Isotopic Fractionation, Hydrogen Bond Geometries
and NMR Parameters ............................................................................................... 204
III. Applications...................................................................................................................... 205
A. H/D Isotope Effects in Strong NHN Hydrogen Bonds ........................................... 205
B. H/D Isotope Effects in OHN Hydrogen Bonded Pyridine-Acid
and Collidine-Acid Complexes .............................................................................. 210
1. Low-Temperature NMR Spectroscopy of Pyridine-Acid Complexes
Dissolved in Liquefied Freon Mixtures ............................................................ 210
2. Geometric Hydrogen Bond Correlations of OHN Hydrogen
Bonded Complexes............................................................................................ 211
3. H/D Isotope Effects on the NMR Parameters of Pyridine-Acid
and Collidine-Acid Complexes ....................................................................... 213
4. H/D Isotopic Fractionation and NMR Parameters
of Pyridine-Acid Complexes ........................................................................... 217
C. Temperature-Induced Solvent H/D Isotope Effects on NMR
Chemical Shifts of FHN Hydrogen Bonds.............................................................. 217
D. H/D Isotope Effects on the NMR Parameters and Geometries
of Coupled Hydrogen Bonds ................................................................................... 222
IV. Conclusions ...................................................................................................................... 226
Acknowledgments ........................................................................................................................ 227
References..................................................................................................................................... 227
For a long time, Nuclear Magnetic Resonance (NMR) spectroscopy has been used to study the
kinetics of hydrogen transfer in condensed phases. As NMR is traditionally regarded as a “slow”
kinetic method, systems exhibiting relatively large barriers for the proton transfer had been studied,
giving rise to kinetic H/D isotope effects.
