Catalysis of redox isomerization of allylic alcohols by [RuClCp(mPTA)2](OSO2CF3)2 and [RuCp(mPTA)2(OH2-κO)](OSO2CF3)3·(H2O)(C4H10O)0.5. Unusual influence of the pH and interaction of phosphate with catalyst on the reaction rate

Beatríz González, Pablo Lorenzo-Luis, Manuel Serrano-Ruiz, Éva Papp, Marianna Fekete, Klára Csépke, Katalin Osz, Ágnes Kathó, Ferenc Joó, Antonio Romerosa

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Abstract

In aqueous solutions at 80 °C, [RuClCp(mPTA)2](OSO2CF3)2 (1) and [RuCp(mPTA)2(OH2-κO)](OSO2CF3)3·(H2O)(C4H10O)0.5 (3) (mPTA: N-methyl-PTA) were found effective catalysts of the redox isomerization of alk-1-en-3-ols to the corresponding ketones, characterized by initial turnover frequencies (TOF) of 162 h-1 (3) and 9.6 h-1 (1) in 1-octen-3-ol isomerization. A sharp maximum of the reaction rate as a function of pH was observed with 1 in phosphate buffer solutions. Kinetic and 31P NMR measurements revealed for the first time in aqueous organometallic catalysis that component(s) of phosphate buffer (most probably HPO42-) strongly interact(s) with the catalyst complexes and this interaction leads to a dramatic loss of the catalytic activity.

Original languageEnglish
Pages (from-to)15-20
Number of pages6
JournalJournal of Molecular Catalysis A: Chemical
Volume326
Issue number1-2
DOIs
Publication statusPublished - Jul 1 2010

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Keywords

  • Allylic alcohols
  • Methyl-PTA
  • Phosphate coordination
  • Redox isomerization
  • Ruthenium

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry

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