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- Title
A Biomimetic Pathway for Vanadium-Catalyzed Aerobic Oxidation of Alcohols: Evidence for a Base-Assisted Dehydrogenation Mechanism.
- Authors
Wigington, Bethany N.; Drummond, Michael L.; Cundari, Thomas R.; Thorn, David L.; Hanson, Susan K.; Scott, Susannah L.
- Abstract
The first step in the catalytic oxidation of alcohols by molecular O2, mediated by homogeneous vanadium(V) complexes [LVV(O)(OR)], is ligand exchange. The unusual mechanism of the subsequent intramolecular oxidation of benzyl alcoholate ligands in the 8-hydroxyquinolinato (HQ) complexes [(HQ)2VV(O)(OCH2C6H4- p-X)] involves intermolecular deprotonation. In the presence of triethylamine, complex 3 (X=H) reacts within an hour at room temperature to generate, quantitatively, [(HQ)2VIV(O)], benzaldehyde (0.5 equivalents), and benzyl alcohol (0.5 equivalents). The base plays a key role in the reaction: in its absence, less than 12 % conversion was observed after 72 hours. The reaction is first order in both 3 and NEt3, with activation parameters Δ H≠=(28±4) kJ mol−1 and Δ S≠=(−169±4) J K−1 mol−1. A large kinetic isotope effect, 10.2±0.6, was observed when the benzylic hydrogen atoms were replaced by deuterium atoms. The effect of the para substituent of the benzyl alcoholate ligand on the reaction rate was investigated using a Hammett plot, which was constructed using σp. From the slope of the Hammett plot, ρ=+(1.34±0.18), a significant buildup of negative charge on the benzylic carbon atom in the transition state is inferred. These experimental findings, in combination with computational studies, support an unusual bimolecular pathway for the intramolecular redox reaction, in which the rate-limiting step is deprotonation at the benzylic position. This mechanism, that is, base-assisted dehydrogenation (BAD), represents a biomimetic pathway for transition-metal-mediated alcohol oxidations, differing from the previously identified hydride-transfer and radical pathways. It suggests a new way to enhance the activity and selectivity of vanadium catalysts in a wide range of redox reactions, through control of the outer coordination sphere.
- Publication
Chemistry - A European Journal, 2012, Vol 18, Issue 47, p14981
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201202499