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Kinetics of Coupled Double Proton and Deuteron Transfer in Hydrogen-Bonded Ribbons of Crystalline Pyrazole-4-carboxylic Acid

Torres, Verónica ; Lopez, Juan-Miguel ; Langer, Uwe ; Buntkowsky, Gerd ; Vieth, Hans-Martin ; Elguero, José ; Limbach, Hans-Heinrich (2021):
Kinetics of Coupled Double Proton and Deuteron Transfer in Hydrogen-Bonded Ribbons of Crystalline Pyrazole-4-carboxylic Acid. (Publisher's Version)
In: Zeitschrift für Physikalische Chemie, 226 (11-12), pp. 1125-1148. De Gruyter, ISSN 0942-9352, e-ISSN 2196-7156,
DOI: 10.26083/tuprints-00019686,
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Item Type: Article
Origin: Secondary publication service
Status: Publisher's Version
Title: Kinetics of Coupled Double Proton and Deuteron Transfer in Hydrogen-Bonded Ribbons of Crystalline Pyrazole-4-carboxylic Acid
Language: English
Abstract:

The proton tautomerism of pyrazole-4-carboxylic acid (PCA) has been studied by a combination of ¹⁵N CPMAS and ²H NMR spectroscopy and relaxometry. Down to 250 K, PCA forms a hydrogen bonded ribbon where adjacent carboxylic and pyrazole groups are linked by an OH···N and an O···HN hydrogen bond, forming either the tautomeric state A or B. Down to about 250 K, the tautomerism is fast on the NMR timescale and degenerate, corresponding to a phase exhibiting dynamic proton disorder. At lower temperatures, a transition to an ordered phase is observed with localized protons, assigned to an all-syn conformation adopting the sequence of tautomeric states ..ABABA.. The longitudinal ¹⁵N relaxation times T₁ of PCA-¹⁵N₂ have been measured at 9.12 MHz (2.1 T). Because of the low field, a chemical shift anisotropy mechanism could be neglected, and the data were analyzed in terms of a dipolar ¹H-¹⁵N relaxation mechanism, yielding the rate constants kHH. The rate constants kHD and kDD were obtained from the measurement and analysis of the ²H T₁ values of PCA-¹⁵N₁ -d₀.₉ and PCA-¹⁵N₁ -d₀.₁ measured at 46.03 MHz. Within the margin of error, no kinetic isotope effects could be detected, in contrast to previous results reported for the very fast tautomerism of solid benzoic acid dimers and the much slower tautomerism of solid 3,5-diphenyl-4-brompyrazole (DPBrP) dimers. The Arrhenius curves of all three systems were simulated using the Bell–Limbach tunneling model. Evidence for a major heavy atom motion for the tautomerism of PCA is obtained, associated with small angle reorientation of PCA molecules around the molecular axis. The observed proton order-disorder transition and the mechanism of the observed rate process are discussed in terms of a coupling of adjacent tautomeric states.

Journal or Publication Title: Zeitschrift für Physikalische Chemie
Journal volume: 226
Number: 11-12
Publisher: De Gruyter
Classification DDC: 500 Naturwissenschaften und Mathematik > 540 Chemie
Divisions: 07 Department of Chemistry > Physical Chemistry
Date Deposited: 01 Oct 2021 11:28
Last Modified: 01 Oct 2021 11:29
DOI: 10.26083/tuprints-00019686
Corresponding Links:
URN: urn:nbn:de:tuda-tuprints-196865
Additional Information:

Keywords: Solid State NMR / Hydrogen Bonded Ribbon / Proton Tautomerism / Order-Disorder Transition / Kinetic Hydrogen/Deuterium Isotope Effects / Heavy Atom Motions and Hydrogen Tunneling

URI: https://tuprints.ulb.tu-darmstadt.de/id/eprint/19686
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