title: Distinct mechanisms for the oxidative addition of chloro-, bromo-, and iodoarenes to a bisphosphine palladium(0) complex with hindered ligands.
abstract: We report an example of a bisphosphine palladium(0) complex with hindered ligands that undergoes oxidative addition of chloro-, bromo-, and iodoarenes in high yield. Addition of PhX (X = I, Br, Cl) to [Pd(Q-phos-tol)2] produced [Pd(Q-phos-tol)(Ph)(I)], [Pd(Q-phos-tol)(Ph)(Br)], and [Pd(Q-phos-tol)(Ph)(Cl)]2. To study the mechanisms of the oxidative addition of the three haloarenes to [Pd(Q-phos-tol)2], we determined the order of the reaction on the concentration of ligand and haloarene. The different haloarenes reacted through different mechanistic pathways. Addition of iodobenzene occurred by irreversible associative displacement of a phosphine. Addition of bromobenzene occurred by rate-limiting dissociation of phosphine. Addition of chlorobenzene occurred by reversible dissociation of phosphine, followed by rate-limiting oxidative addition. The mechanism of exchange of ligands from the Pd(0)L2 was also studied. The rate constant value for dissociation of ligand calculated from ligand exchange experiments is in agreement with the value calculated through experiments on oxidative addition.
authors.affiliation: Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107, USA.
authors.forename: Fabiola
authors.initials: F
authors.lastname: Barrios-Landeros
authors.forename: John F
authors.initials: JF
authors.lastname: Hartwig
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*
chemical_list: D001555:Benzene Derivatives; D006846:Hydrocarbons, Halogenated; D008024:Ligands; D010720:Phosphines; D010165:Palladium