Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 5, Issue 7, Pages 1126-1130Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jz500192k
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Funding
- U.S. Department of Energy, Basic Energy Sciences [FG02-84-ER13289]
- Graduate Fellowship Program (DOE SCGF) [DE-AC05-06OR23100]
- National Science Foundation, Division of Chemistry, Analytical and Surface Science [CHE-0952790]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0952790] Funding Source: National Science Foundation
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Selective oxidative reactions promoted by gold depend critically on controlling the coverage and stability of adsorbed intermediates, as well as promoting specific bond activations of those intermediates. We demonstrate that acetate, a common intermediate in the oxidation of olefins, aldehydes, and alcohols, is destabilized by 7-10 kcal/mol by coadsorbed oxygen relative to its stability on the clean gold surface. The amount of destabilization depends on the oxygen coverage. Peak temperatures of products indicative of oxygen-assisted and clean-surface bond activation differ by up to 130 K. Experiments with d(3)-acetate show a kinetic isotope effect of 6.9 at 400 K, indicating that the rate-limiting step of the low temperature oxygen-assisted reaction is gamma-CH bond breaking. This clearly demonstrates that coadsorbed oxygen activates gamma-CH bonds on gold and suggests that an oxygen-assisted activation may also occur for beta-CH bonds crucial in oxygen-assisted alcohol coupling on metallic gold catalysts, as predicted by theory.
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