Hydrogen/Deuterium Isotope Effects on the NMR Chemical Shifts and Geometries of Intermolecular Low-Barrier Hydrogen-Bonded Complexes

Autor:	Gleb S. Denisov, Sergei N. Smirnov, Hans-Heinrich Limbach, Nikolai S. Golubev, Parwin Schah-Mohammedi, Hans Benedict
Rok vydání:	1996
Předmět:	Deuterium NMR Hydrogen Hydrogen bond Chemical shift Inorganic chemistry chemistry.chemical_element General Chemistry Carbon-13 NMR Biochemistry Catalysis Colloid and Surface Chemistry chemistry Deuterium Kinetic isotope effect Proton NMR Physical chemistry
Zdroj:	Journal of the American Chemical Society. 118:4094-4101
ISSN:	1520-5126 0002-7863
DOI:	10.1021/ja953445+
Popis:	In this paper we describe H/D isotope effects on the chemical shifts of intermolecular hydrogen-bonded complexes exhibiting low barriers for proton transfer, as a function of the position of the hydrogen bond proton. For this purpose, low-temperature (100−150 K) 1H, 2H, and 15N NMR experiments were performed on solutions of various protonated and deuterated acids AL (L = H, D) and pyridine-15N (B) dissolved in a 2:1 mixture of CDClF2/CDF3. In this temperature range, the regime of slow proton and hydrogen bond exchange is reached, leading to resolved NMR lines for each hydrogen-bonded species as well as for different isotopic modifications. The experiments reveal the formation of 1:1, 2:1, and 3:1 complexes between AH(D) and B. The heteronuclear scalar 1H−15N coupling constants between the hydrogen bond proton and the 15N nucleus of pyridine show that the proton is gradually shifted from the acid to pyridine-15N when the proton-donating power of the acid is increased. H/D isotope effects on the chemical sh...
Databáze:	OpenAIRE
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