Journal of the American Chemical Society p. 4553 - 4561 (1989)
Update date:2022-08-16
Topics:
Brainard, Robert L.
Peterson, Cynthia G.
Madix, Robert J.
Allyl alcohol reacts with clean and oxygen-covered Cu(110) surfaces to produce propanal, acrolein, n-propyl alcohol, and hydrogen under ultrahigh-vacuum conditions.Very small amounts of propylene and water are also formed.This pattern of reactivity contrasts sharply to the selective oxidation to acrolein observed on Ag(110).On the clean Cu(110) surface allyl alcohol undergoes O-H cleavage to form the surface alkoxide CH2=CHCH2O(a) and H(a).The results suggest that the olefin in this species undergoes partial hydrogenation to the surface-bound oxametallacycles (-CH2CH2CH2O-)(a) and (-CH-(CH3)CH2O-)(a) and complete hydrogenation to CH3CH2CH2O(a).Propanal forms at 320 K via further reaction of these oxametallacycles.Evidence for a ?-bonded allyl oxide CH2=CHCH2O(a), which is more stable than n-propoxide (CH3CH2CH2O(a)) toward β-hydride elimination, is presented.This allyl oxide decomposes at 370 K to form acrolein.The interaction of the double bond with the surface apparently restricts the interaction of the β-C-H bond with the surface and increases the stability of this species.Propanal, acrolein and H2 are formed at 435 K by a process thought to involve the thermal decomposition of (-CH2CH2CH2O-)(a) by a β-hydride elimination pathway.This dehydrogenation pathway exhibits an activation energy 8 kcal/mol greater than for acyclic alkoxides.The conversion of allyl alcohol to propanal and propyl alcohol obviously involves the hydrogenation of the double bond which, by comparison, does not occur for propylene coadsorbed with hydrogen under similar conditions on this surface.Clearly, the hydroxyl group in allyl alcohol facilitates the hydrogenation of its olefin group by tethering the doublebond to the surface at temperatures higher than the normal desorption temperature of olefins.
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(1989)