| Résumé | Photolysis of hydrocarbon solutions of di-tert-butyldiazomethane and fluoroorganic halides, RfX, in the presence of hexamethylditin yields persistent organofluorine substituted di-tert-butylmethyl radicals, RfĊ(CMe3)2. EPR parameters for these radicals are reported. Despite the fact that aFβ is essentially the same for CF3Ċ(CMe3)2 and CF3CF2Ċ(CMe3)2 it is concluded that the CF3 group in the latter radical is locked in the eclipsed position with respect to the Cα 2pz orbital, while in the former radical the CF3 group rotates freely on the EPR time scale. Perpendicular benzyls are produced when Rf is a fluorophenyl group. Similar experiments with di-tert-butylketene have yielded the first perpendicular alkanoylalkyl radicals, RfCOĊ(CMe3)2. © 1978 American Chemical Society. |
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