title: Ligand-modulated palladium oxidation catalysis: mechanistic insights into aerobic alcohol oxidation with the Pd(OAc)(2)/pyridine catalyst system.
abstract: Pd(OAc)(2):pyridine (1:4) is an efficient catalyst system for the oxidation of alcohols with molecular oxygen. A mechanistic study of this reaction reveals that pyridine promotes the aerobic oxidation of palladium(0) but inhibits the oxidation of alcohol by palladium(II). Kinetic results reveal that turnover-limiting substrate oxidation consists of (i) formation of a palladium(II)-alkoxide, (ii) pyridine dissociation, and (iii) beta-hydride elimination. These results provide a framework for the design and/or screening of more effective aerobic oxidation catalysts.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI 53706, USA.
authors.forename: Bradley A
authors.initials: BA
authors.lastname: Steinhoff
authors.forename: Shannon S
authors.initials: SS
authors.lastname: Stahl