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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

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Published copy (DOI)

Author(s)

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

Department/unit(s)

Publication details

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

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 HPO4 2-) strongly interact(s) with the catalyst complexes and this interaction leads to a dramatic loss of the catalytic activity.

    Research areas

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

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