title: Mechanism of Pd-Catalyzed Decarbonylation of Biomass-Derived Hydrocinnamic Acid to Styrene following Activation as an Anhydride.
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.
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Manuel A
authors.initials: MA
authors.lastname: Ortuño
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Büşra
authors.initials: B
authors.lastname: Dereli
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Cramer
mesh_terms: D000812:Anhydrides / Q000737:chemistry*; D002384:Catalysis; D004735:Energy Transfer; D007700:Kinetics; D008024:Ligands; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D010666:Phenylpropionates / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry; D011789:Quantum Theory; D020058:Styrene / Q000138:chemical synthesis*
chemical_list: D000812:Anhydrides; D008024:Ligands; D010666:Phenylpropionates; D010720:Phosphines; D020058:Styrene; C035253:3-phenylpropionic acid; D010165:Palladium