title: Methanolysis of thioamide promoted by a simple palladacycle is accelerated by 10(8) over the methoxide-catalyzed reaction.
abstract: Palladacycle 1 catalyzes the methanolytic cleavage of N-methyl-N-(4-nitrophenyl)thiobenzamide (4) via a mechanism involving formation of a Pd-bound tetrahedral intermediate (TI). The rate constant for decomposition of the complex formed between 1, methoxide, and 4 is 9.3 s(-1) at 25 °C; this reaction produces methyl thiobenzoate and N-methyl-4-nitroaniline. The ratio of the second-order rate constant for the catalyzed reaction, given as k(cat)/K(d), relative to that of the methoxide-promoted reaction is 3 × 10(8), representing a very large catalysis of thioamide bond cleavage by a synthetic metal complex.
authors.affiliation: Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, Canada K7L 3N6.
authors.forename: C Tony
authors.initials: CT
authors.lastname: Liu
authors.forename: Christopher I
authors.initials: CI
authors.lastname: Maxwell
authors.forename: Stephanie G
authors.initials: SG
authors.lastname: Pipe
authors.forename: Alexei A
authors.initials: AA
authors.lastname: Neverov
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Mosey
authors.forename: R Stan
authors.initials: RS
authors.lastname: Brown
mesh_terms: D002384:Catalysis; D007700:Kinetics; D008697:Methane / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013854:Thioamides / Q000737:chemistry*
chemical_list: D013854:Thioamides; D010165:Palladium; D008697:Methane