Correlation Engine 2.0
Clear Search sequence regions


  • adduct (1)
  • catalysis (1)
  • ligand (3)
  • mono (1)
  • palladium (3)
  • phosphines (3)
  • xanthenes (2)
  • xantphos (2)
  • Sizes of these terms reflect their relevance to your search.

    Kinetic, spectroscopic, crystallographic, and computational studies probing a Pd-catalyzed C-H arylation reaction reveal that mono-oxidation of the bis-phosphine ligand is critical for the formation of the active catalyst. The bis-phosphine mono-oxide is shown to be a hemilabile, bidentate ligand for palladium. Isolation of the oxidative addition adduct, with structural elucidation by X-ray analysis, showed that the mono-oxide was catalytically competent, giving the same reaction rate in the productive reaction as the Pd(II)/xantphos precursor. A dual role for the carboxylate base in both catalyst activation and reaction turnover was demonstrated, along with the inhibiting effect of excess phosphine ligand. The generality of the role of phosphine mono-oxide complexes in Pd-catalyzed coupling processes is discussed.

    Citation

    Yining Ji, R Erik Plata, Christopher S Regens, Michael Hay, Michael Schmidt, Thomas Razler, Yuping Qiu, Peng Geng, Yi Hsiao, Thorsten Rosner, Martin D Eastgate, Donna G Blackmond. Mono-Oxidation of Bidentate Bis-phosphines in Catalyst Activation: Kinetic and Mechanistic Studies of a Pd/Xantphos-Catalyzed C-H Functionalization. Journal of the American Chemical Society. 2015 Oct 21;137(41):13272-81

    Expand section icon Mesh Tags

    Expand section icon Substances


    PMID: 26461028

    View Full Text