Volumes of activation for the cycloaddition reactions of phenylhalocarbenes to alkenes

Nicholas J. Turro, Masami Okamoto, Ian Gould, Robert A. Moss, Witold Ławrynowicz, Linda M. Hadel

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The absolute rate constants for the cycloaddition reactions of three arylhalocarbenes to two alkenes have been measured as a function of pressure in the range 0.1 to 203 MPa. In all cases the observed rate constants were found to increase with increasing pressure. The magnitude of the derived activation volumes falls in the range of -10 to -18 cm3/mol and does not depend on solvent. The results rule out a late, two-bond transition state and a bipolar single-bond transition state but are consistent with the reversible formation of a carbene-alkene complex or an early one- or two-bond transition state.

Original languageEnglish (US)
Pages (from-to)4973-4976
Number of pages4
JournalJournal of the American Chemical Society
Volume109
Issue number16
StatePublished - 1987
Externally publishedYes

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Cycloaddition
Cycloaddition Reaction
Alkenes
Olefins
Rate constants
Chemical activation
Pressure
carbene
single bond

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Turro, N. J., Okamoto, M., Gould, I., Moss, R. A., Ławrynowicz, W., & Hadel, L. M. (1987). Volumes of activation for the cycloaddition reactions of phenylhalocarbenes to alkenes. Journal of the American Chemical Society, 109(16), 4973-4976.

Volumes of activation for the cycloaddition reactions of phenylhalocarbenes to alkenes. / Turro, Nicholas J.; Okamoto, Masami; Gould, Ian; Moss, Robert A.; Ławrynowicz, Witold; Hadel, Linda M.

In: Journal of the American Chemical Society, Vol. 109, No. 16, 1987, p. 4973-4976.

Research output: Contribution to journalArticle

Turro, NJ, Okamoto, M, Gould, I, Moss, RA, Ławrynowicz, W & Hadel, LM 1987, 'Volumes of activation for the cycloaddition reactions of phenylhalocarbenes to alkenes', Journal of the American Chemical Society, vol. 109, no. 16, pp. 4973-4976.
Turro, Nicholas J. ; Okamoto, Masami ; Gould, Ian ; Moss, Robert A. ; Ławrynowicz, Witold ; Hadel, Linda M. / Volumes of activation for the cycloaddition reactions of phenylhalocarbenes to alkenes. In: Journal of the American Chemical Society. 1987 ; Vol. 109, No. 16. pp. 4973-4976.
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