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

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

Research output: Contribution to journalArticle

Abstract

Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh 3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (?H = 195 ± 41 kJ mol-1; ?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 - 1 Feb 2006

Keywords

  • Cyclometallation
  • Density functional theory
  • Hydride ligands
  • Murai reaction
  • Phosphine ligands
  • Ruthenium complexes

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