Epr study of tertiary cyclic perfluorinated radicals: Methylcyclopentyl and decalyl radicals

EPR spectroscopy was used to study new cyclic perfluorinated radicals, namely, methylcyclopentyl and decalyl radicals obtained by the photolysis of the corresponding bromides in the presence of dicarboranylmercury. The EPR spectrum of the perfluorocyclopentyl radical shows line broadening, which indicates an insufficiently high rate of inversion of the five-membered ring. The constants for coupling with the -fluorine atoms in the decalyl radical indicate considerable comparison of the radical site. The motion of the substituants inthe decalyl radical is hindered. The much lower dimerization rate constant in comparison with the corresponding acyclic radicals may be related to the stereochemical rigidity of the radical site.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2371–2374, October, 1989.