Modified [(IPr)Pd(R-acac)Cl] Complexes: Influence of the acac Substitution on the Catalytic Activity in Aryl Amination

Nicolas Marion, Oscar Navarro, Edwin D. Stevens, Elise C. Ecarnot, Andrew Bell, Dino Amoroso, Steven Patrick Nolan

Research output: Contribution to journalArticlepeer-review

Abstract

The synthesis of a series of [(IPr)Pd(R-acac)Cl] precatalysts (acac=acetylacetonato: IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), where the acac ligand on palladium has been systematically modified through terminal substitution, is reported. The following substituted acac ligands are employed in this study: dibenzoylmethanato (dbm), benzoylacelonato (bac), tetramethylheptanedionato (tmhd), and hexafluoroace tylacetonato (hfac). Full spectroscopic characterization of the new complexes is provided along with X-ray studies for three of these. Investigation of their catalytic activity in cross-coupling is also presented through a comparative study in an aryl amination reaction. The catalytic results show a strong correlation between the increased steric bulk of the acac substituents and an increased activation rate of the precatalyst, going from the acac to the tmhd ligand. This observation, along with the inertness of the Iliac compound, seems to support our previous proposal for the activation mechanism of these complexes under cross-coupling conditions.

Original languageEnglish
Pages (from-to)841-846
Number of pages6
JournalChemistry-An Asian Journal
Volume5
Issue number4
DOIs
Publication statusPublished - 2010

Keywords

  • activation
  • amination
  • cross-coupling
  • N-heterocyclic
  • carbenes
  • palladium
  • CROSS-COUPLING REACTIONS
  • N-HETEROCYCLIC CARBENE
  • TEMPERATURE SUZUKI-MIYAURA
  • ROOM-TEMPERATURE
  • PALLADIUM(II) COMPLEXES
  • (NHC)PD(ALLYL)CL NHC
  • REDUCTIVE ELIMINATION
  • OXIDATIVE ADDITION
  • BUCHWALD-HARTWIG
  • ACETONE DBA

Fingerprint

Dive into the research topics of 'Modified [(IPr)Pd(R-acac)Cl] Complexes: Influence of the acac Substitution on the Catalytic Activity in Aryl Amination'. Together they form a unique fingerprint.

Cite this