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Computational study of carbostannylation implicating bimetallic catalysis involving 'AuI-vinyl-PdII' species
journal contribution
posted on 2023-05-18, 05:41 authored by Alireza AriafardAlireza Ariafard, Rajabi, NA, Atashgah, MJ, Allan CantyAllan Canty, Brian YatesBrian YatesWe 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.
History
Publication title
ACS CatalysisVolume
4Pagination
860-869ISSN
2155-5435Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
United States of AmericaRights statement
Copyright 2014 American Chemical SocietyRepository Status
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