Computational study of carbostannylation implicating bimetallic catalysis involving "auI-Vinyl-PdII" species

Alireza Ariafard, Nasir Ahmad Rajabi, Mona Jalali Atashgah, Allan J. Canty, Brian F. Yates

Research output: Contribution to journalArticlepeer-review

9 Citations (SciVal)


We have investigated computationally the gold and palladium cocatalyzed reaction of alkynes with vinylstannane. Our work has involved a careful and thorough exploration of different mechanistic possibilities. We find that palladium acting alone as a catalyst leads to a very high reaction barrier, consistent with the experimental observation that there is no reaction in the presence of just palladium. However, the involvement of a gold(I) complex lowers the reaction barrier considerably, and the vinylstannylation reaction can proceed with a modest activation energy of about 10 kcal/mol. Our key finding is that the introduction of the gold complex avoids the formation of high-energy structures involving vinyl species in a trans arrangement on palladium. Our work confirms the role of intermediates containing both palladium and gold as suggested by Blum. For the gold-palladium cocatalyzed reaction, we also investigated an alternative mechanism suggested by Blum. With some modifications, this mechanism has a slightly higher reaction barrier, but if it does occur, then we predict a strong dependency on the counterion, in agreement with related experimental findings.

Original languageEnglish
Pages (from-to)860-869
Number of pages10
JournalACS Catalysis
Issue number3
Early online date14 Feb 2014
Publication statusPublished - 7 Mar 2014


  • bimetallic catalysis
  • density functional theory (DFT)
  • gold
  • palladium
  • reaction mechanism
  • vinylstannylation

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)


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