Theoretical Studies of the Mechanism of Aerobic Alcohol Oxidation with Palladium Catalyst Systems

Density functional theory (DFT) was applied to a comprehensive mechanistic study of the Pd(II)-catalyzed oxidation of alcohols by molecular oxygen. Both parts of the catalytic cycle, i.e., the oxidative dehydrogenation of the substrate and the regeneration of the catalyst by the co-oxidant, molecula...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Organometallics 2005-02, Vol.24 (5), p.885-893
Hauptverfasser: Privalov, Timofei, Linde, Christian, Zetterberg, Krister, Moberg, Christina
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:Density functional theory (DFT) was applied to a comprehensive mechanistic study of the Pd(II)-catalyzed oxidation of alcohols by molecular oxygen. Both parts of the catalytic cycle, i.e., the oxidative dehydrogenation of the substrate and the regeneration of the catalyst by the co-oxidant, molecular oxygen, were studied. The catalytic cycle under consideration consists of intramolecular deprotonation, β-hydride elimination, and migratory insertion steps, and it is relevant for a wide class of catalytic systems. In particular, a Pd(II) cyclometalated system was addressed and qualitatively compared with the Uemura system (Pd(OAc)2/pyridine) and with the Pd−carbene system. Geometries of the intermediate complexes and relative Gibbs free energies were identified along the proposed reaction path with the help of computational methods. The transition state for the β-hydride elimination, which is the highest point on the energy profile of the catalytic cycle, was identified.
ISSN:0276-7333
1520-6041
1520-6041
DOI:10.1021/om049141q