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 trans-bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-κ2O,O′)bis{4-(N-tert-butyl(oxyl)amino)perfluoroarene-κO}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.
Highlights
The use of organofluorine compounds has had a huge impact on the main areas of modern chemistry, such as the development of new functional materials and pharmaceuticals with unique properties [1,2,3,4]
Using octafluorotoluene 1a and pentafluorobenzonitrile 1b as examples, we demonstrated a of the nitroxide groups with the Cu2+ ion
Using octafluorotoluene 1a and pentafluorobenzonitrile 1b as examples, we demonstrated a new synthetic approach for obtaining functionalized fluorinated phenyl tert-butyl nitroxides by sequential substitution of a fluorine atom in polyfluorinated arenes with tert-butylamine and oxidation of resultant tert-butylaniline with meta-chloroperoxybenzoic acid (m-CPBA)
Summary
The use of organofluorine compounds has had a huge impact on the main areas of modern chemistry, such as the development of new functional materials and pharmaceuticals with unique properties [1,2,3,4]. To devise new approaches to their synthesis, we applied nucleophilic substitution reactions of a fluorine atom in a series of polyfluorinated aromatic compounds. This idea has been especially fruitful in nitroxide chemistry. To coupling, and their complexation with M(hfac) have allowed Iwamura et al to obtaineta series obtain a series of molecular magnets capable of cooperative magnetic ordering at. Substitution of a fluorine atom [14] to the synthesis of fluorinated N-tert-butyl aryl nitroxides This approach was found to generate highly stable nitroxide radicals in almost quantitative yields.
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