Mechanism of Pd(OAc)2/DMSO-catalyzed aerobic alcohol oxidation:: Mass-transfer-limitation effects and catalyst decomposition pathways

Pd(OAc)(2) in DMSO is an effective catalyst for the aerobic oxidation of alcohols and numerous other organic substrates. Kinetic studies of the catalytic oxidation of primary and secondary benzylic alcohol substrates provide fundamental insights into the catalytic mechanism. In contrast to the conclusion reached in our earlier study (J. Am. Chem. Soc. 2002, 124, 766-767), we find that Pd(II)-mediated alcohol oxidation is the turnover-limiting step of the catalytic reaction. At elevated catalyst loading, however, the rate of catalytic turnover is limited by the dissolution of oxygen gas into solution. This mass-transfer rate is measured directly by using gas-uptake methods, and it correlates with the maximum rate observed during catalysis. Initial-rate studies were complemented by kinetic analysis of the full-reaction timecourses at different catalyst concentrations. Kinetic fits of these traces reveal the presence of unimolecular and bimolecular catalyst decomposition pathways that compete with productive catalytic turnover.