Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
EPR Spectra and Structure of the Radical Cations of Fluorinated Ethylenes and Propenes
Yoshiteru ItagakiMasaru ShiotaniAkinori HasegawaHisao Kawazoe
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1998 Volume 71 Issue 11 Pages 2547-2554

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Abstract

EPR spectra for the radical cations of a series of fluorinated ethylenes and propenes, generated by irradiation with γ-rays in halocarbon solid matrices, have been observed at low temperature. The spectra consist of a hyperfine structure with a nearly axial symmetry mainly due to fluorine nuclei. For the trifluoro olefin cations, CF2=CFX+ (X = H, CH3, or CF3), the experimental spectra were successfully analyzed in terms of the three 19F nuclei with coaxial parallel components. This may strongly suggest a planar structure for the radical cations, similarly to the case of the CF2=CF2+ cation already reported. On the other hand, for mono- and di-fluoro olefin radical cations, it is difficult to conclude the planar structure unequivocally from the experimental 19F and 1H hf splittings. Thus, the optimized geometry of the radical cations was calculated by an ab initio MO method. In contrast with the ethylene cation and the propene cation, having nonplanar twisted structures, the fluorinated ethylene and propene cations are concluded to have planar structures. Calculations at the INDO levels including the evaluation of interatomic dipole-dipole interactions were done for the geometries of the radical cations optimized by the ab initio method. The calculated results strongly support the EPR spectra observed and assigned to the radical cations.

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© 1998 The Chemical Society of Japan
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