Volumes of activation for β-elimination and related reactions of chromium(III)-alkyl complexes in aqueous solutions

Haim Cohen, Rudi van Eldik, Wolfgang Gaede, Achim Gerhard, Sara Goldstein, Gidon Czapski, Dan Meyerstein

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8 Scopus citations

Abstract

A systematic study of the effect of pressure on the decomposition of chromium(III)-alkyl complexes via β-elimination was undertaken. It was found that the elimination of OR (RH or alkyl) is characterized by a negative volume of activation, whereas the elimination of NH3 exhibits a positive volume of activation. These values are interpreted in terms of early and late transition states, respectively. In addition, the effect of pressure on the spontaneous and acid-catalyzed heterolysis of [(H2O)5CrIII-CH2CH(OH)2]2+ and [(H2O)5CrIII-H]2+ was studied. The results, when compared to literature data, indicate that the volumes of activation for heterolysis depend strongly on the intimate nature of the mechanism.

Original languageEnglish
Pages (from-to)57-61
Number of pages5
JournalInorganica Chimica Acta
Volume227
Issue number1
DOIs
StatePublished - 1 Dec 1994

Keywords

  • Alkyl complexes
  • Chromium complexes
  • Volume of activation
  • β-Elimination

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