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

doi:10.1016/0020-1693(94)04134-2

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

Research output: Contribution to journal › Article › peer-review

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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)₅Cr^III-CH₂CH(OH)₂]²⁺ and [(H₂O)₅Cr^III-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 language	English
Pages (from-to)	57-61
Number of pages	5
Journal	Inorganica Chimica Acta
Volume	227
Issue number	1
DOIs	https://doi.org/10.1016/0020-1693(94)04134-2
State	Published - 1 Dec 1994
Externally published	Yes

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

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.",

keywords = "Alkyl complexes, Chromium complexes, Volume of activation, β-Elimination",

author = "Haim Cohen and {van Eldik}, Rudi and Wolfgang Gaede and Achim Gerhard and Sara Goldstein and Gidon Czapski and Dan Meyerstein",

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.",

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AU - van Eldik, Rudi

AU - Gaede, Wolfgang

AU - Gerhard, Achim

AU - Goldstein, Sara

AU - Czapski, Gidon

AU - Meyerstein, Dan

N1 - 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.

PY - 1994/12/1

Y1 - 1994/12/1

N2 - 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.

AB - 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.

KW - Alkyl complexes

KW - Chromium complexes

KW - Volume of activation

KW - β-Elimination

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

Abstract

Bibliographical note

Keywords

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