The Solvent Effects on Kinetics and Mechanism of Zinc or Cadmium Halide Catalyzed Reactions of Hydrosilanes with Hydroxylic Reagents

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Title:The Solvent Effects on Kinetics and Mechanism of Zinc or Cadmium Halide Catalyzed Reactions of Hydrosilanes with Hydroxylic Reagents
Creators:
Chruściel, Jerzy J.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 69, 12, pp. 2281-2296
Uncontrolled Keywords:Reaction mechanisms, Dehydrocoupling, Solvent effects, Hydrosilanes, Hydroxylic reagents, Silanes, Silanols, Nucleophilic substitutions

Abstract

The effect of solvent composition on reaction rates was studied by a kinetic method for reactions of Et<sub>3</sub>SiH with Ph<sub>2</sub>Si(OH)<sub>2</sub> in the presence of ZnCl<sub>2</sub> in a mixture of DMF and THF or Et<sub>3</sub>SiH with PhCOOH and cadmium bromide CdBr<sub>2</sub> in DMF-1,4-dioxane and DMF-THF. A decrease in reaction rates with decreasing polarity of the medium (and its dielectric constant) has been observed. The kinetic order of dehydrocoupling reaction with respect to DMF was determined from kinetic studies. The constants of nucleophilic catalysis with DMF (λ) were found. The role of DMF in the mechanism of dehydrocoupling of hydrosilanes with hydroxylic reagents in the presence of ZnX<sub>2</sub> and CdX<sub>2</sub> halides (X = Cl, Br, I) is discussed. <p>

Title:The Solvent Effects on Kinetics and Mechanism of Zinc or Cadmium Halide Catalyzed Reactions of Hydrosilanes with Hydroxylic Reagents
Creators:
Chruściel, Jerzy J.
Uncontrolled Keywords:Reaction mechanisms, Dehydrocoupling, Solvent effects, Hydrosilanes, Hydroxylic reagents, Silanes, Silanols, Nucleophilic substitutions
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:69
Number:12
Page Range:pp. 2281-2296
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20042281UNSPECIFIED
ID Code:2336
Item Type:Article
Deposited On:06 Feb 2009 17:17
Last Modified:06 Feb 2009 16:17

Citation

Chruściel, Jerzy J. (2004) The Solvent Effects on Kinetics and Mechanism of Zinc or Cadmium Halide Catalyzed Reactions of Hydrosilanes with Hydroxylic Reagents. Collection of Czechoslovak Chemical Communications, 69 (12). pp. 2281-2296. ISSN 0010-0765

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