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Aromatic S(N)(F)-Approach to Fluorinated Phenyl tert-Butyl Nitroxides
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(ox...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6943699/ https://www.ncbi.nlm.nih.gov/pubmed/31817965 http://dx.doi.org/10.3390/molecules24244493 |
Sumario: | 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-κ(2)O,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 J(Cu–R) reaching 53 cm(−1). |
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