Different types of hydrogen bonds in 2‐substituted pyrroles and 1‐vinyl pyrroles as monitored by 1H, 13C and 15N NMR spectroscopy and ab initio calculations
- 31 October 2005
- journal article
- research article
- Published by Wiley in Magnetic Resonance in Chemistry
- Vol. 44 (1), 59-65
- https://doi.org/10.1002/mrc.1727
Abstract
According to the 1H, 13C and 15N NMR spectroscopic data and ab initio calculations, the strong NH···O intramolecular hydrogen bond in the Z‐isomers of 2‐(2‐acylethenyl)pyrroles causes the decrease in the absolute size of the 1J(N,H) coupling constant by 2 Hz in CDCl3 and by 4.5 Hz in DMSO‐d6, the deshielding of the proton and nitrogen by 5–6 and 15 ppm, respectively, and the lengthening of the NH link by 0.025 Å. The NH···N intramolecular hydrogen bond in the 2(2′‐pyridyl)pyrrole leads to the increase of the 1J(N,H) coupling constant by 3 Hz, the deshielding of the proton by 1.5 ppm and the lengthening of the NH link by 0.004 Å. The CH···N intramolecular hydrogen bond in the 1‐vinyl‐2‐(2′‐pyridyl)‐pyrrole results in the increase of the 1J(C,H) coupling constant by 5 Hz, the deshielding of the proton by 1 ppm and the shortening of the CH link by 0.003 Å. Different behavior of the coupling constants and length of the covalent links under the hydrogen bond influence originate from the different nature of the hydrogen bonding (predominantly covalent or electrostatic), which depends in turn on the geometry of the hydrogen bridge. The Fermi‐contact mechanism only is responsible for the increase of the coupling constant in the case of the predominantly electrostatic hydrogen bonding, whereas both Fermi‐contact and paramagnetic spin‐orbital mechanisms bring about the decrease of coupling constant in the case of the predominantly covalent hydrogen bonding Copyright © 2005 John Wiley & Sons, Ltd.Keywords
This publication has 39 references indexed in Scilit:
- NMR Parameters and Geometries of OHN and ODN Hydrogen Bonds of Pyridine–Acid ComplexesChemistry – A European Journal, 2004
- Influence of the C—H· · ·N intramolecular interaction on the spatial structures and 1H and 13C NMR parameters of heteroaryl vinyl ethers and sulfidesMagnetic Resonance in Chemistry, 2003
- C—H···X (X = N, O, S) intramolecular interaction in 1-vinyl-2-(2′-heteroaryl)pyrroles as monitored by 1H and 13C NMR spectroscopyMagnetic Resonance in Chemistry, 2001
- Hydrogen bonding in complexes of adenosine and 4-thiouridine: a low-temperature NMR studyMagnetic Resonance in Chemistry, 2001
- Internucleotide Scalar Couplings Across Hydrogen Bonds in Watson−Crick and Hoogsteen Base Pairs of a DNA TriplexJournal of the American Chemical Society, 1999
- Proximity Effects on Nuclear Spin-Spin Coupling Constants. 1. J(CH) Couplings in the Vicinity of an Atom Bearing Lone PairsThe Journal of Physical Chemistry, 1994
- Electron affinities of the first-row atoms revisited. Systematic basis sets and wave functionsThe Journal of Chemical Physics, 1992
- Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculationsJournal of the American Chemical Society, 1990
- Intramolecular interactions in N‐vinyl‐2‐arylpyrroles and ‐2‐heteroarylpyrroles by 1H and 13C NMRMagnetic Resonance in Chemistry, 1990
- Nitrogen NMR spectroscopy: Application to some substituted pyrrolesMagnetic Resonance in Chemistry, 1976