Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: models for the Murai reaction

Rodolphe F. R. Jazzar, Maurizio Varrone, Andrew D. Burrows, Stuart A. Macgregor, Mary F. Mahon, Michael K. Whittlesey

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16 Citations (Scopus)

Abstract

Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh3)(2)(Co)(NC4H3C(O)CH3)H] {cis-NH (1) and trans-NH (2) have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to I upon heating via a dissociative pathway (Delta H++ = 195 +/- 41 kJ mol(-1); Delta S++ = 232 +/- 62 J mol(-1) K-1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2'-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions.
Original languageEnglish
Pages (from-to)815-820
Number of pages6
JournalInorganica Chimica Acta
Volume359
Issue number3
DOIs
Publication statusPublished - Feb 2006

Keywords

  • Molecular structure (of isomeric ruthenium(II) N
  • O-coordinated acetylpyrrolyl hydrido carbonyl bis(phosphine) complex related to Murai coupling catalysts)
  • O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes as models for catalytic intermediates in Murai coupling reaction)
  • O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complexes)
  • crystal structure ruthenium acetylpyrrolyl hydride carbonyl phosphine isomer
  • O-coordinated acetylpyrrolyl hydrido carbonyl bis(triphenylphosphine) complex isomers as models for catalytic intermediates in Murai coupling reaction)
  • Transition state structure (in isomerization of ruthenium(II) N
  • ruthenium acetylpyrrolyl hydride carbonyl phosphine complex prepn structure isomerization
  • Isomerization (of ruthenium(II) N
  • isomerization ruthenium acetylpyrrolyl hydride carbonyl phosphine complex thermodn
  • Isomerization enthalpy (of isomeric ruthenium(II) N
  • Activation entropy (for isomerization of isomeric ruthenium(II) N
  • Crystal structure
  • Murai coupling catalyst intermediate ruthenium acetylpyrrolyl hydride carbonyl phosphine
  • Coupling reaction catalysts (Murai
  • prepn. of ruthenium(II) N

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