Kinetics and Mechanism of the Acetate-Catalyzed Heterolysis of the Metal-Carbon σ Bond of (α-Hydroxyalkyl)Chromium(III) Complexes. Effects of Nonparticipating Ligands, Temperature, and Pressure

Haim Cohen; Wolfgang Gaede; Achim Gerhard; Dan Meyerstein; Rudi van Eldik

doi:10.1021/ic00044a024

Kinetics and Mechanism of the Acetate-Catalyzed Heterolysis of the Metal-Carbon σ Bond of (α-Hydroxyalkyl)Chromium(III) Complexes. Effects of Nonparticipating Ligands, Temperature, and Pressure

Haim Cohen, Wolfgang Gaede, Achim Gerhard, Dan Meyerstein, Rudi van Eldik

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Abstract

The acetate-catalyzed heterolysis reaction of two (a-hydroxyalkyl)chromium(III) complexes, Cr^III-CH₂OH and Cr^III-C(CH₃)₂OH, with three types of nonparticipating ligands (H₂O)₅Cr-R²⁺, irons-([15]aneN₄)(H₂O)Cr-R²⁺, and cis-(nta)(H₂O)Cr-R^-, has been studied as a function of acetate concentration, temperature, and pressure. The reported rate and activation parameters demonstrate that the catalytic effect results from a trans-labilization effect by coordinated acetate and involves the attack by a solvent water molecule on the metal-carbon bond. The positive volumes of activation support the operation of a dissociatively activated heterolysis mechanism, which is in line with the suggested labilization effect by coordinated acetate.

Original language	English
Pages (from-to)	3805-3809
Number of pages	5
Journal	Inorganic Chemistry
Volume	31
Issue number	18
DOIs	https://doi.org/10.1021/ic00044a024
State	Published - 1992
Externally published	Yes

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title = "Kinetics and Mechanism of the Acetate-Catalyzed Heterolysis of the Metal-Carbon σ Bond of (α-Hydroxyalkyl)Chromium(III) Complexes. Effects of Nonparticipating Ligands, Temperature, and Pressure",

abstract = "The acetate-catalyzed heterolysis reaction of two (a-hydroxyalkyl)chromium(III) complexes, CrIII-CH2OH and CrIII-C(CH3)2OH, with three types of nonparticipating ligands (H2O)5Cr-R2+, irons-([15]aneN4)(H2O)Cr-R2+, and cis-(nta)(H2O)Cr-R-, has been studied as a function of acetate concentration, temperature, and pressure. The reported rate and activation parameters demonstrate that the catalytic effect results from a trans-labilization effect by coordinated acetate and involves the attack by a solvent water molecule on the metal-carbon bond. The positive volumes of activation support the operation of a dissociatively activated heterolysis mechanism, which is in line with the suggested labilization effect by coordinated acetate.",

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

year = "1992",

doi = "10.1021/ic00044a024",

language = "אנגלית",

volume = "31",

pages = "3805--3809",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "18",

}

Kinetics and Mechanism of the Acetate-Catalyzed Heterolysis of the Metal-Carbon σ Bond of (α-Hydroxyalkyl)Chromium(III) Complexes. Effects of Nonparticipating Ligands, Temperature, and Pressure. / Cohen, Haim; Gaede, Wolfgang; Gerhard, Achim et al.
In: Inorganic Chemistry, Vol. 31, No. 18, 1992, p. 3805-3809.

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

TY - JOUR

T1 - Kinetics and Mechanism of the Acetate-Catalyzed Heterolysis of the Metal-Carbon σ Bond of (α-Hydroxyalkyl)Chromium(III) Complexes. Effects of Nonparticipating Ligands, Temperature, and Pressure

AU - Cohen, Haim

AU - Gaede, Wolfgang

AU - Gerhard, Achim

AU - Meyerstein, Dan

AU - van Eldik, Rudi

PY - 1992

Y1 - 1992

N2 - The acetate-catalyzed heterolysis reaction of two (a-hydroxyalkyl)chromium(III) complexes, CrIII-CH2OH and CrIII-C(CH3)2OH, with three types of nonparticipating ligands (H2O)5Cr-R2+, irons-([15]aneN4)(H2O)Cr-R2+, and cis-(nta)(H2O)Cr-R-, has been studied as a function of acetate concentration, temperature, and pressure. The reported rate and activation parameters demonstrate that the catalytic effect results from a trans-labilization effect by coordinated acetate and involves the attack by a solvent water molecule on the metal-carbon bond. The positive volumes of activation support the operation of a dissociatively activated heterolysis mechanism, which is in line with the suggested labilization effect by coordinated acetate.

AB - The acetate-catalyzed heterolysis reaction of two (a-hydroxyalkyl)chromium(III) complexes, CrIII-CH2OH and CrIII-C(CH3)2OH, with three types of nonparticipating ligands (H2O)5Cr-R2+, irons-([15]aneN4)(H2O)Cr-R2+, and cis-(nta)(H2O)Cr-R-, has been studied as a function of acetate concentration, temperature, and pressure. The reported rate and activation parameters demonstrate that the catalytic effect results from a trans-labilization effect by coordinated acetate and involves the attack by a solvent water molecule on the metal-carbon bond. The positive volumes of activation support the operation of a dissociatively activated heterolysis mechanism, which is in line with the suggested labilization effect by coordinated acetate.

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SN - 0020-1669

VL - 31

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 18

ER -

Kinetics and Mechanism of the Acetate-Catalyzed Heterolysis of the Metal-Carbon σ Bond of (α-Hydroxyalkyl)Chromium(III) Complexes. Effects of Nonparticipating Ligands, Temperature, and Pressure

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