Aromatic SN F-Approach to Fluorinated Phenyl tert-Butyl Nitroxides

Evgeny Tretyakov, Pavel Fedyushin, Elena Panteleeva, Larisa Gurskaya, Tatyana Rybalova, Artem Bogomyakov, Elena Zaytseva, Maxim Kazantsev, Inna Shundrina, Victor Ovcharenko

Research output: Contribution to journalArticlepeer-review

Abstract

The interaction of octafluorotoluene (1a), as well as pentafluorobenzonitrile (1b) with tert-butylamine, followed by the oxidation of thus formed tert-butylanilines (2a,b) with meta-chloroperoxybenzoic acid led to functionalized perfluorinated phenyl tert-butyl nitroxides [namely, 4-(N-tert-butyl(oxyl)amino)heptafluorotoluene (3a) and 4-(N-tert-butyl(oxyl)amino)tetrafluorobenzonitrile (3b)] with nearly quantitative total yields. The molecular and crystal structures of nitroxide 3a were proved by single crystal X-ray diffraction analysis. The radical nature of both nitroxides was confirmed by ESR data. The interaction of Cu(hfac)2 with the obtained nitroxides 3a,b gave corresponding transbis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ2O,O0)bis{4-(N-tert-butyl(oxyl)amino)perfluoroareneκO}copper (II) complexes ([Cu(hfac)2(3a)2] and [Cu(hfac)2(3b)2]). X-ray crystal structure analysis showed square bipyramid coordination of a centrally symmetric Cu polyhedron with the axial positions occupied by oxygen atoms of the nitroxide groups. Magnetic measurements revealed intramolecular ferromagnetic exchange interactions between unpaired electrons of Cu(II) ions and paramagnetic ligands, with exchange interaction parameters JCu–R reaching 53 cm−1

Original languageEnglish
Article number4493
Number of pages14
JournalMolecules
Volume24
Issue number24
DOIs
Publication statusPublished - 8 Dec 2019

Keywords

  • Aromatic nucleophilic substitution
  • Copper-nitroxide complexes
  • Fluoroarenes
  • Magneto-structural correlations
  • Nitroxides
  • Tert-butylanilines
  • magneto-structural correlations
  • MECHANISM
  • tert-butylanilines
  • COPPER(II)
  • COMPLEXES
  • aromatic nucleophilic substitution
  • nitroxides
  • HYDROGEN-BONDS
  • fluoroarenes
  • TRANSITION
  • NITRONYL NITROXIDE
  • FERROMAGNETIC INTERACTIONS
  • RADICALS
  • MAGNETIC-PROPERTIES
  • EXCHANGE
  • copper-nitroxide complexes
  • Crystallography, X-Ray
  • Coordination Complexes/chemistry
  • Oxygen/chemistry
  • Copper/chemistry
  • Molecular Structure
  • Oxidation-Reduction
  • Halogenation
  • Ligands
  • Fluorocarbons/chemistry

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