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Electron structure and reactivity of organofluorine compounds. 4. AMI calculations of anion radicals of primary, secondary, and tertiary perfluoroalkyl chlorides, bromides, and iodides

  • G. D. Rempel'
  • Yu. A. Borisov
  • N. I. Raevskii
  • S. M. Igumnov
  • I. N. Rozhkov
Physical Chemistry

Abstract

Calculations were carried out using the semiempirical quantum chemical AMI method for anion radicals (AR) of the perfluoroalkyl halides (RFX): CF3X, CF3CF2X, (CF3)2-CFX, and (CF3)3CX for X=Cl, Br, and I. All the AR's studied are thermally stable. The electron affinity of the perfluoroalkyl halides, and consequently, the thermal stability of their AR's increases in the series from F-methyl to F-tertbutyl halides and from the chlorides to bromides and iodides. During formation of an AR the spin density is preferentially localized on the σ* orbital of the Cα−X bond which leads to an increase in the distance between these atoms. Dissociation of the AR of tert-perfluorobutyl iodide to a perfluorocarbanion and an I atom is thermodynamically more favorable than dissociation with formation of a perfluoroalkyl radical and I.

Keywords

Chloride Bromide Thermal Stability Iodide Quantum Chemical 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Plenum Publishing Corporation 1990

Authors and Affiliations

  • G. D. Rempel'
    • 1
  • Yu. A. Borisov
    • 1
  • N. I. Raevskii
    • 1
  • S. M. Igumnov
    • 1
  • I. N. Rozhkov
    • 1
  1. 1.A. N. Nesmeyanov Institute of Heteroorganic CompoundsAcademy of Sciences of the USSRMoscow

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