Theoretical structures and stabilities of C3H5+ and C3H2F3+ cations

Michael McAllister, Thomas T. Tidwell, Michael R. Peterson, I. Csizmadia

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Abstract

The structures and energies of C3H2F3+ isomers have been calculated, and at the MP4(SDQ)/6-31G**// HF/6-31G* + ZPVE level fluorine migration converting CH2=C+CF3 (3) to the allylic cation CH2=CFCF2+ (4) is exothermic by 31.5 kcal/mol, with a barrier involving a bridged fluoronium ion of only 6.1 kcal/mol. Rearrangement of 3 to CHF=CHCF2+ (16) is exothermic by 44.9 kcal/mol and occurs by a multistep process including a 1,3-fluorine migration with no barrier higher than 0.3 kcal/mol. Comparative studies of C3H5+ are also reported. It is concluded that 3 is a good candidate for an experimental search for fluorine migration in carbocations.

Original languageEnglish
Pages (from-to)575-580
Number of pages6
JournalJournal of Organic Chemistry
Volume56
Issue number2
Publication statusPublished - 1991

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Fluorine
Cations
Isomers
Ions

ASJC Scopus subject areas

  • Organic Chemistry

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McAllister, M., Tidwell, T. T., Peterson, M. R., & Csizmadia, I. (1991). Theoretical structures and stabilities of C3H5+ and C3H2F3+ cations. Journal of Organic Chemistry, 56(2), 575-580.

Theoretical structures and stabilities of C3H5+ and C3H2F3+ cations. / McAllister, Michael; Tidwell, Thomas T.; Peterson, Michael R.; Csizmadia, I.

In: Journal of Organic Chemistry, Vol. 56, No. 2, 1991, p. 575-580.

Research output: Contribution to journalArticle

McAllister, M, Tidwell, TT, Peterson, MR & Csizmadia, I 1991, 'Theoretical structures and stabilities of C3H5+ and C3H2F3+ cations', Journal of Organic Chemistry, vol. 56, no. 2, pp. 575-580.
McAllister, Michael ; Tidwell, Thomas T. ; Peterson, Michael R. ; Csizmadia, I. / Theoretical structures and stabilities of C3H5+ and C3H2F3+ cations. In: Journal of Organic Chemistry. 1991 ; Vol. 56, No. 2. pp. 575-580.
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AB - The structures and energies of C3H2F3+ isomers have been calculated, and at the MP4(SDQ)/6-31G**// HF/6-31G* + ZPVE level fluorine migration converting CH2=C+CF3 (3) to the allylic cation CH2=CFCF2+ (4) is exothermic by 31.5 kcal/mol, with a barrier involving a bridged fluoronium ion of only 6.1 kcal/mol. Rearrangement of 3 to CHF=CHCF2+ (16) is exothermic by 44.9 kcal/mol and occurs by a multistep process including a 1,3-fluorine migration with no barrier higher than 0.3 kcal/mol. Comparative studies of C3H5+ are also reported. It is concluded that 3 is a good candidate for an experimental search for fluorine migration in carbocations.

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