Electronic structure and reaction ability of organic fluorine compounds

By semiempirical quantum-chemical method AM1 calculations of anion-radicals (AR) - perfluoroalkyl halides (RFX) : CF3X, CF3CF2X, (CF3)2CFX, (CF3)3CX for X=Cl,Br,I, are performed. All AR considered are thermodynamically stable. Affinity to electron of perfluoroalkyl halides and, accordingly, thermodynamic stability of their AR increase from F-methyl- to F-tert. butyl halides and from chlorides to bromides and iodides. When AR are formed spin density is mainly localized on σ* - orbital of Cα-X bond, which results in the increase of distance between the atoms. The dissociation of tert. perfluorobutyl iodide AR for perfluorocarbanion and I atom is more expedient from thermodynamic viewpoint than dissociation with the formation of perfluoroalkyl radical and I-