Measuring the kinetic isotope effect at natural isotopic abundances for discriminating between the homogeneous and heterogeneous catalytic mechanisms in the Heck and Suzuki reactions

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• 作者：A. A. Kurokhtina ; E. V. Larina ; A. F. Schmidt
• 关键词：kinetic isotope effect homogeneous and heterogeneous catalysis ; Suzuki reaction ; Heck reaction
• 刊名：Kinetics and Catalysis
• 出版年：2016
• 出版时间：January 2016
• 年：2016
• 卷：57
• 期：1
• 页码：32-38
• 全文大小：294 KB
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• 作者单位：A. A. Kurokhtina (1)
  E. V. Larina (1)
  A. F. Schmidt (1)
  
  1. Faculty of Chemistry, Irkutsk State University, Irkutsk, 664003, Russia
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Catalysis
  Physical Chemistry
  Russian Library of Science
  
• 出版者：MAIK Nauka/Interperiodica distributed exclusively by Springer Science+Business Media LLC.
• ISSN：1608-3210

文摘

The kinetic isotope effect (KIE) at the natural abundances of bromine and carbon isotopes in the substrates of the Heck and Suzuki reactions have been investigated to determine the true nature of catalyst in these reactions. Data processing has demonstrated that statistically significant differences between KIE values for the Suzuki reaction of nonactivated bromobenzene are observed upon the replacement of the soluble catalyst precursor with the insoluble one. This finding unambiguously indicates that the reaction takes place on heterogeneous palladium species. Similar experiments on the Heck reaction have demonstrated that the KIE values are insensitive to the nature of the catalyst precursor, which is consistent with the true homogeneous mechanism of catalysis.