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Russian Chemical Bulletin

, Volume 63, Issue 12, pp 2591–2598 | Cite as

The structure of protonated 3-pyridyl-substituted 5-amino-1H-1,2,4-triazoles: an experimental and theoretical study

  • V. M. Chernyshev
  • A. V. Astakhov
  • V. B. Rybakov
  • A. V. Chernysheva
  • E. V. Tarasova
Full Articles
  • 63 Downloads

Abstract

The molecular and crystal structures and tautomerism of protonated isomeric 3-pyridyl- substituted 5-amino-1H-1,2,4-triazoles were studied within the framework of density function- al theory and by X-ray analysis. According to B3LYP/6-311++G(2d,2p) calculations of six possible tautomeric forms A-F, tautomers A with the N-protonated pyridine moiety are predominant in the gas phase. 5-Amino-4H-1-onium compounds (tautomers D) of higher polarity are next in stability; their relative energies decrease as follows: 3-pyridin-4-yl-, 3-pyridin-3-yl-, and 3-pyridin-2-yl-5-amino-4H-1,2,4-triazol-1-onium cation. A comparison of experimental 13C NMR spectra of tautomers A and D with their NMR spectra calculated by the GIAO method showed that both tautomeric forms can coexist in comparable amounts in DMSO solutions. Tautomers A and D were detected by X-ray analysis in crystals of 5-amino-3-(pyrid- in-2-yl)-1H-1,2,4-triazolium salts.

Key words

pyridyl-substituted 5-amino-1H-1,2,4-triazoles protonation tautomerism molecular and crystal structure 

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Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • V. M. Chernyshev
    • 1
  • A. V. Astakhov
    • 1
  • V. B. Rybakov
    • 2
  • A. V. Chernysheva
    • 1
  • E. V. Tarasova
    • 1
  1. 1.Platov South-Russian State Polytechnic UniversityRostov RegionRussian Federation
  2. 2.M. V. Lomonosov Moscow State UniversityMoscowRussian Federation

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