Electron structure and reactivity of organofluorine compounds. 4. AMI calculations of anion radicals of primary,secondary, and tertiary perfluoroalkyl chlorides,bromides, and iodides |
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Authors: | G D Rempel' Yu A Borisov N I Raevskii S M Igumnov I N Rozhkov |
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Institution: | (1) A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow |
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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 * orbital of the C –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–.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1064–1068, May, 1990. |
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