Trinuclear Pd₃O₂ intermediate in aerobic oxidation catalysis.
The activation of O2 is a key step in selective catalytic aerobic oxidation reactions mediated by transition metals. The bridging trinuclear palladium species, [(LPd(II))3(μ(3)-O)2](2+) (L=2,9-dimethylphenanthroline), was identified during the [LPd(OAc)]2(OTf)2-catalyzed aerobic oxidation of 1,2-propanediol. Independent synthesis, structural characterization, and catalytic studies of the trinuclear compound show that it is a product of oxygen activation by reduced palladium species and is a competent intermediate in the catalytic aerobic oxidation of alcohols. The formation and catalytic activity of the trinuclear Pd3O2 species illuminates a multinuclear pathway for aerobic oxidation reactions catalyzed by Pd complexes.
Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, CA 94305-5080 (USA).
Andrew J
AJ
Ingram
Diego
D
Solis-Ibarra
Richard N
RN
Zare
Robert M
RM
Waymouth
D000438:Alcohols / Q000737:chemistry; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry; D018360:Crystallography, X-Ray; D008698:Mesylates / Q000737:chemistry; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*
D000438:Alcohols; D056831:Coordination Complexes; D008698:Mesylates; D010165:Palladium; C048320:palladium oxide; C012077:trifluoromethanesulfonic acid
aerobic oxidation; homogeneous catalysis; mass spectrometry; palladium; reaction mechanisms