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.
- bimetallic catalysis
- density functional theory (DFT)
- reaction mechanism
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