Kinetics and mechanism of coupled synthesis of cyclohexanecarboxylic acid

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• 作者：A. Yu. Putin (1)
  E. Yu. Bychkova (1)
  K. V. Trunilina (1)
  A. Yu. Zakgeim (1)
  E. A. Katsman (1)
  O. N. Shishilov (1)
  N. S. Akhmadullina (2)
  I. V. Oshanina (1)
  O. N. Temkin (1)
  L. G. Bruk (1)
  
  1. Lomonosov Moscow State University of Fine Chemical Technologies ; Moscow ; Russia
  2. Baikov Institute of Metallurgy and Materials Sciences ; Russian Academy of Sciences ; Moscow ; Russia
  
• 关键词：coupled process ; hydrocarboxylation of cyclohexene ; cyclohexanecarboxylic acid ; palladium hydride complex ; hypotheses about mechanism ; kinetic isotope effect ; kinetic model
• 刊名：Russian Journal of Physical Chemistry A, Focus on Chemistry
• 出版年：2015
• 出版时间：March 2015
• 年：2015
• 卷：89
• 期：3
• 页码：359-368
• 全文大小：484 KB
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• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Physical Chemistry
  Russian Library of Science
  
• 出版者：MAIK Nauka/Interperiodica distributed exclusively by Springer Science+Business Media LLC.
• ISSN：1531-863X

文摘

The effect of the nature of the anion in a palladium salt on a coupled process involving the oxidation of CO and hydrocarboxylation of cyclohexene in the PdX2-CuBr2-THF-H2O system was studied. The kinetics was investigated under the steady-state conditions. The kinetic isotope effects (H2O/D2O) for the rates of formation of CO2 and cyclohexanecarboxylic acid were measured. The mechanism of the coupled processes of hydrocarboxylation of cyclohexene involving the formation of palladium hydride complexes and their transformations was suggested. The kinetic model of the processes was obtained.