Surface-Driven Keto-Enol Tautomerization: Atomistic Insights into Enol Formation and Stabilization Mechanisms

被引:31
作者
Attia, Smadar [1 ,2 ]
Schmidt, Marvin-Christopher [1 ]
Schroeder, Carsten [1 ]
Pessier, Pascal [1 ]
Schauermann, Swetlana [1 ]
机构
[1] Christian Albrechts Univ Kiel, Inst Phys Chem, Max Eyth Str 2, D-24118 Kiel, Germany
[2] Max Planck Gesell, Fritz Haber Inst, Dept Chem Phys, Faradayweg 4-6, D-14195 Berlin, Germany
基金
欧洲研究理事会;
关键词
carbonyl compounds; keto-enol tautomerization on metals; model heterogeneous catalysis; scanning tunneling microscopy; vibrational spectroscopy on surfaces; SCANNING-TUNNELING-MICROSCOPY; METHYL ACETOACETATE; HYDROGENATION; ACROLEIN; BONDS; METHYLACETOACETATE; CHEMISTRY; OXIDATION; ALCOHOLS; PYRUVATE;
D O I
10.1002/anie.201808453
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Tautomerisation of simple carbonyl compounds to their enol counterparts on metal surfaces is envisaged to enable an easier route for hydrogenation of the C=O bond in heterogeneously catalyzed reactions. To understand the mechanisms of enol formation and stabilization over catalytically active metal surfaces, we performed a mechanistic study on keto-enol tautomerization of a monocarbonyl compound acetophenon over Pt(111) surface. By employing infrared reflection adsorption spectroscopy in combination with scanning tunneling microscopy, we found that enol can be formed by building a ketone-enol dimer, in which one molecule in the enol form is stabilized through hydrogen bonding to the carbonyl group of the second ketone molecule. Based on the investigations of the co-adsorption behavior of acetophenone and hydrogen, we conclude that keto-enol tautomerization occurs in the intramolecular process and does not involve hydrogen transfer through the surface hypothesized previously.
引用
收藏
页码:16659 / 16664
页数:6
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