Imidazole based ruthenium(IV) complexes as highly efficient bifunctional catalysts for the redox isomerization of allylic alcohols in aqueous medium: Water as cooperating ligand

Josefina Díez, José Gimeno, Agustí Lledós, Francisco J. Suárez, Cristian Vicent

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43 Citations (Scopus)

Abstract

Bis-allyl ruthenium(IV) complexes containing 1,3 azole β-N-H protic ligands [Ru(ν 3:ν 3-C 10H 16)Cl 2L] (C 10H 16 = 2,7-dimethylocta-2,6-diene- 1,8-diyl) (L = imidazole (1a), benzimidazole (1b)), and N-methylimidazole (1c) are highly active precatalysts in the redox isomerization of allylic alcohols into carbonyl compounds in aqueous medium and in the absence of base. A wide series of primary and secondary allylic alcohols can be isomerized into the corresponding carbonyl compounds. Remarkably, complex 1b has been found to be the most efficient catalyst reported to date for the isomerization of 1-octen-3- ol in water leading to a turnover frequency (TOF) value of 60 000 h-1. Moreover, catalyst 1b can be recycled remaining active up to seven cycles. Density functional theory (DFT) calculations give evidence that the hydroxo complexes derived from 1a-c species can be formed in aqueous solution and that they can act as the catalytic active species in a bifunctional catalyzed process. This study demonstrate that in water the participation of the β-N-H protic group of the 1,3-azole ligands in the bifunctional catalysis is not required, provided that a water molecule can act as cooperating ligand. © 2012 American Chemical Society.
Original languageEnglish
Pages (from-to)2087-2099
JournalACS Catalysis
Volume2
Issue number10
DOIs
Publication statusPublished - 5 Oct 2012

Keywords

  • Allylic alcohols
  • Aqueous medium
  • Cooperating ligands
  • DFT calculations
  • Redox isomerization
  • Ruthenium catalysts

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