Computational Study of the Palladium-Catalyzed Carbonylative Synthesis of Aromatic Acid Chlorides: The Synergistic Effect of PtBu3and CO on Reductive Elimination

Jeffrey S. Quesnel, Salvador Moncho Escriva, Kai E.O. Ylijoki, Gerardo Martin Torres, Edward Brothers, Ashfaq A. Bengali, Bruce A. Arndtsen

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12 Citations (Scopus)


We describe herein computational studies on the unusual ability of Pd(PtBu3)2to catalyze formation of highly reactive acid chlorides from aryl halides and carbon monoxide. These show a synergistic role of carbon monoxide in concert with the large cone angle PtBu3that dramatically lowers the barrier to reductive elimination. The tertiary structure of the phosphine is found to be critical in allowing CO association and the generation of a high energy, four coordinate (CO)(PR3)Pd(COAr)Cl intermediate. The stability of this complex, and the barrier to elimination, is highly dependent upon phosphine structure, with the tertiary steric bulk of PtBu3favoring product formation over other ligands. These data suggest that even difficult reductive eliminations can be rapid with CO association and ligand manipulation. This study also represents the first detailed exploration of all the steps involved in palladium-catalyzed carbonylation reactions with simple phosphine ligands, including the key rate-determining steps and palladium(0) catalyst resting state in carbonylations.

Original languageEnglish
Pages (from-to)15107-15118
Number of pages12
JournalChemistry - A European Journal
Issue number42
Publication statusPublished - 2016



  • acid chloride
  • carbonylation
  • density functional calculations
  • palladium
  • reductive elimination

ASJC Scopus subject areas

  • Chemistry(all)

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