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
Externally publishedYes

Bibliographical note

Funding Information:
This study was supported by a grant from the German-Israel Foundation, GIF, Jerusalem, Israel and by a grant from the Budgeting and Planning Committee of the Council of Higher Education and the Israel Atomic Energy Commission. R.v.E. acknowledges support from the Deutsche Forschungsgemeinschaft, Fonds der Chemischen Industrie and Volkswagen-Stiftung. D.M. expresses his thanks to Mrs Irene Evens for her ongoing interest and support.

Keywords

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

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