Reaction of Paramagnetic Synthon, Lithiated 4,4,5,5-Tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide, with Cyclic Aldonitrones of the Imidazole Series

Svyatoslav E. Tolstikov, Evgeny V. Tretyakov, Dmitry E. Gorbunov, Irina F. Zhurko, Matvey V. Fedin, Galina V. Romanenko, Artem S. Bogomyakov, Nina P. Gritsan, Dmitry G. Mazhukin

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)

Abstract

It was shown that dipole-stabilized paramagnetic carbanion lithiated 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide can be attached in a nucleophilic manner to either isolated or conjugated aldonitrones of the 2,5-dihydroimidazole 3-oxide and 2H-imidazole 1-oxide series to afford adducts the subsequent oxidation of which leads to polyfunctional mono- and diradicals. According to XRD, at least two polymorphic modifications can be formed during crystallization of the resulting paramagnetic compounds, and for each of them, geometric parameters of the molecules are similar. An EPR spectrum of the diradical in frozen toluene has a complicated lineshape, which can be fairly well reproduced by using X-ray diffraction structural analysis and the following set of parameters: D=14.9 mT, E=1.7 mT; tensor a(14N)=[0.260 0.260 1.625] mT, two equivalent tensors for the nitronyl nitroxide moiety a(14N)=[0.198 0.198 0.700] mT, and g≈2.007. According to our DFT and ab initio calculations, the intramolecular exchange in the diradical is very weak and most likely ferromagnetic.

Original languageEnglish
Pages (from-to)14598-14604
Number of pages7
JournalChemistry - A European Journal
Volume22
Issue number41
DOIs
Publication statusPublished - 2016

Keywords

  • ab initio calculations
  • density functional calculations
  • diradicals
  • EPR spectroscopy
  • X-ray diffraction

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