Refinement of labile hydrogen positions based on DFT calculations of 1 H NMR chemical shifts: comparison with X-ray and neutron diffraction methods

Organic & Biomolecular Chemistry
Michael G SiskosIoannis P Gerothanassis

Abstract

Numerous gas phase electron diffraction, ultra-fast electron diffraction, X-ray and neutron diffraction experiments on β-dicarbonyl compounds exhibiting enol-enol tautomeric equilibrium, with emphasis on acetylacetone and dibenzoylmethane, have so far been reported with conflicting results on the structural details of the O-HO intramolecular hydrogen bond and resulted in alternative hypotheses on the intramolecular hydrogen bond potential function either a double minimum potential corresponding to two tautomeric forms in equilibrium or a single symmetrical one. We demonstrate herein, firstly, that the DFT calculated OH 1H NMR chemical shifts of acetylacetone and dibenzoylmethane exhibit a strong linear dependence on the computed OO hydrogen bond length of ∼-50 ppm Å-1 and as a function of the O-HO bond angle of ∼1 ppm per degree, upon the transfer of the hydrogen atom from the ground state toward the transition state. Secondly, the refinement of labile hydrogen atomic positions in intramolecular hydrogen bonds based on the root-mean-square deviation between experimentally determined and DFT calculated 1H NMR chemical shifts in solution can provide high resolution structures of O-H and O(H)O bond lengths and O-HO bond angles wit...Continue Reading

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Citations

Jan 29, 2020·Physical Chemistry Chemical Physics : PCCP·Shengmin Zhou, Lu Wang
Oct 6, 2017·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Eleni AlexandriIoannis P Gerothanassis
Jun 23, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Saima H MariIoannis P Gerothanassis
Aug 17, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Themistoklis VenianakisIoannis P Gerothanassis
Jul 17, 2021·Physical Chemistry Chemical Physics : PCCP·Sana FatimaIoannis P Gerothanassis

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