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

^*Corresponding author for this work

School of Nursing

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

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)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

Keywords

Alkyl complexes
Chromium complexes
Volume of activation
β-Elimination

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10.1016/0020-1693(94)04134-2

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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",

year = "1994",

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doi = "10.1016/0020-1693(94)04134-2",

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T1 - Volumes of activation for β-elimination and related reactions of chromium(III)-alkyl complexes in aqueous solutions

AU - Cohen, Haim

AU - van Eldik, Rudi

AU - Gaede, Wolfgang

AU - Gerhard, Achim

AU - Goldstein, Sara

AU - Czapski, Gidon

AU - Meyerstein, Dan

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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AN - SCOPUS:0343550249

SN - 0020-1693

VL - 227

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EP - 61

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 1

ER -

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

Abstract

Keywords

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