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Mono-oxidation of bidentate bis-phosphines in catalyst activation: kinetic and mechanistic studies of a Pd/xantphos-catalyzed C-H functionalization

Academic Article
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Overview

authors

  • Ji, Y.
  • Plata, R. E.
  • Regens, C. S.
  • Hay, M.
  • Schmidt, M.
  • Razler, T.
  • Qiu, Y.
  • Geng, P.
  • Hsiao, Y.
  • Rosner, T.
  • Eastgate, M. D.
  • Blackmond, Donna

publication date

  • October 2015

journal

  • Journal of the American Chemical Society  Journal

abstract

  • 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.

subject areas

  • Catalysis
  • Crystallography, X-Ray
  • Kinetics
  • Magnetic Resonance Spectroscopy
  • Oxidation-Reduction
  • Palladium
  • Phosphines
  • Xanthenes
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Identity

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/jacs.5b01913

PubMed ID

  • 26461028
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Additional Document Info

start page

  • 13272

end page

  • 13281

volume

  • 137

issue

  • 41

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