Research output: Contribution to journal › Article › peer-review
NMR parameters and geometries of OHN and ODN hydrogen bonds of pyridine-acid complexes. / Limbach, Hans Heinrich; Pietrzak, Mariusz; Sharif, Shasad; Tolstoy, Peter M.; Shenderovich, Ilya G.; Smirnov, Sergei N.; Golubev, Nikolai S.; Denisov, Gleb S.
In: Chemistry - A European Journal, Vol. 10, No. 20, 11.10.2004, p. 5195-5204.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - NMR parameters and geometries of OHN and ODN hydrogen bonds of pyridine-acid complexes
AU - Limbach, Hans Heinrich
AU - Pietrzak, Mariusz
AU - Sharif, Shasad
AU - Tolstoy, Peter M.
AU - Shenderovich, Ilya G.
AU - Smirnov, Sergei N.
AU - Golubev, Nikolai S.
AU - Denisov, Gleb S.
PY - 2004/10/11
Y1 - 2004/10/11
N2 - 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.
AB - 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.
KW - Acid-base complexes
KW - Hydrogen bonds
KW - Isotope effects
KW - NMR parameters
UR - http://www.scopus.com/inward/record.url?scp=7044231571&partnerID=8YFLogxK
U2 - 10.1002/chem.200400212
DO - 10.1002/chem.200400212
M3 - Article
C2 - 15372662
AN - SCOPUS:7044231571
VL - 10
SP - 5195
EP - 5204
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 20
ER -
ID: 43112731