Abstract
All elementary steps in the mechanism of Pd-catalyzed decarbonylation of hydrocinnamic acid through formation of a mixed anhydride species have been characterized through electronic structure calculations. Oxidative addition of the mixed anhydride to a singly or doubly ligated Pd is followed by decarbonylation, alkene formation, and catalyst regeneration. Metal-assisted deprotonation of the alkyl-Pd species by a coordinated carboxylate is predicted to be the rate-determining step; theory suggests that bulkier phosphine ligands (e.g., P(o-Tol)3) reduce the free energy of activation substantially, while variation of the auxiliary anhydride has little influence on efficiency.
Original language | English (US) |
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Pages (from-to) | 4124-4131 |
Number of pages | 8 |
Journal | Inorganic chemistry |
Volume | 55 |
Issue number | 9 |
DOIs | |
State | Published - May 2 2016 |
Bibliographical note
Publisher Copyright:© 2016 American Chemical Society.