title: Correlation of relative rates of PdCl(2) oxidation of functionalized acyclic alkenes versus alkene ionization potentials, HOMOs, and LUMOs.
abstract: Investigations of the title reaction, carried out by plotting logs of the relative reaction rates vs IPs, vs HOMOs, and vs LUMOs, reveal multiple nearly parallel lines of correlation with small negative slopes in each. Overall, the natural grouping into monosubstituted and disubstituted alkenes gives better correlations than that obtained by using all alkenes. Comparison with analogous plots for other reactions indicates that the mechanism for this reaction has similarities to that for hydroboration, the major difference being that the lines in the plots for hydroboration have positive slopes, indicating an electrophilic rate-determining step involving the pi electrons, while those for the title reaction have small negative slopes, indicating a nucleophilic rate-determining step. Of the two reaction mechanisms proposed for the title reaction, only one has a nucleophilic attack at the complexed alkene as the rate-determining step, and therefore, this work supports that reaction mechanism.
authors.affiliation: Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, USA.
authors.forename: D J
authors.initials: DJ
authors.lastname: Nelson
authors.forename: R
authors.initials: R
authors.lastname: Li
authors.forename: C
authors.initials: C
authors.lastname: Brammer