Role of Surface-Bound Intermediates in the Oxygen-Assisted Synthesis of Amides by Metallic Silver and Gold
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- 作者：Cassandra G. F. Siler ; Bingjun Xu ; Robert J. Madix ; Cynthia M. Friend
- 刊名：The Journal of the American Chemical Society
- 出版年：2012
- 出版时间：August 1, 2012
- 年：2012
- 卷：134
- 期：30
- 页码：12604-12610
- 全文大小：350K
- 年卷期：v.134,no.30(August 1, 2012)
- ISSN：1520-5126
文摘
A general mechanism for the oxygen-assisted synthesis of amides over metallic gold and silver surfaces has been derived from the study of acetaldehyde and dimethylamine in combination with previous work, allowing detailed comparison of the two surfaces鈥?reactivities. Facile acetylation of dimethylamine by acetaldehyde occurs with high selectivity on oxygen-covered silver and gold (111) crystals via a common overall mechanism with different rate-limiting steps on the two metals. Adsorbed atomic oxygen activates the N鈥揌 bond of the amine leading to the formation of an adsorbed amide, which attacks the carbonyl carbon of the aldehyde, forming an adsorbed hemiaminal. Because aldehydes are known to form readily from partial oxidation of alcohols, our mechanism also provides insight into the related catalytic coupling of alcohols and amines. The hemiaminal 尾-H eliminates to form the coupled amide product. On silver, 尾-H elimination from the hemiaminal is rate-limiting, whereas on gold desorption of the amide is the slow step. Silver exhibits high selectivity for the coupling reaction for adsorbed oxygen concentrations between 0.01 and 0.1 monolayer, whereas gold exhibits selectivity more strongly dependent on oxygen coverage, approaching 100% at 0.03 monolayer. The selectivity trends and difference in rate-limiting steps are likely due to the influence of the relative stability of the adsorbed hydroxyl groups on the two surfaces. Low surface coverages of oxygen lead to the highest selectivity. This study provides a general framework for the oxygen-assisted coupling of alcohols and aldehydes with amines over gold- and silver-based catalysts in either the vapor or the liquid phase.