Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 61, Pages 15226-15238Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202102554
Keywords
density-functional theory; isomerization; palladium; reaction mechanisms; stereoselectivity
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Funding
- Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy [EXC-2033-390677874-RESOLV, SFB TRR88]
- bilateral DST-DFG scheme [INT/FRG/DFG/P-05/2017/GO 853/12-1]
- UGC, India
- Fonds der chemischen Industrie
- Projekt DEAL
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In this study, it was found that a significant amount of products are formed via the dinuclear pathway during isomerization of allyl arenes, esters, amides, ethers, and alcohols. The dissociation barrier towards mononuclear Pd species is relatively high, and once the catalyst enters the energetically more favorable mononuclear pathway, only a low barrier has to be overcome towards irreversible deactivation.
In a combined experimental and computational study, the isomerization activity of the dinuclear palladium(I) complex [Pd-I(mu-Br)((PBu3)-Bu-t)](2) towards allyl arenes, esters, amides, ethers, and alcohols has been investigated. The calculated energy profiles for catalyst activation for two alternative dinuclear and mononuclear catalytic cycles, and for catalyst deactivation are in good agreement with the experimental results. Comparison of experimentally observed E/Z ratios at incomplete conversion with calculated kinetic selectivities revealed that a substantial amount of product must form via the dinuclear pathway, in which the isomerization is promoted cooperatively by two palladium centers. The dissociation barrier towards mononuclear Pd species is relatively high, and once the catalyst enters the energetically more favorable mononuclear pathway, only a low barrier has to be overcome towards irreversible deactivation.
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