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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Density Functional Study of the Palladium Acetate Catalyzed Wacker Reaction in Acetic Acid
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Density Functional Study of the Palladium Acetate Catalyzed Wacker Reaction in Acetic Acid

机译：乙酸钯催化瓦克反应在乙酸中的密度泛函研究

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摘要

In the Wacker process, palladium acetate complexes catalyze the homogeneous reaction of ethylene and water to form acetaldehyde. We have studied the mechanism of this reaction in detail, using density functional theory computational methods. The putative most active catalyst is a dimer complex, which has been modeled by clusters of two palladium ions coordinated by acetate ligands. The active site is formed by one of the palladium ions. In the Wacker process as catalyzed by palladium acetate, ethylene coordinates to palladium. Next, coupling with hydroxyl species from the solution takes place in an outer-sphere mechanism. A series of hydrogen transfers, in which terminal acetate participates, converts the hydroxyethyl ligand into acetaldehyde.Finally, the product desorbs. The overall reaction enthalpy is exothermic. One of the hydrogen transfers, the step that results in acetaldehyde formation, is the rate-determining step. This step costs 61 kJ/mol. All reactions presumably take place within the coordination sphere, and thus hydrogen from the solvent is not incorporated into the product. Solvent effects are explicitly taken into account in all steps.
机译：在瓦克工艺中，乙酸钯络合物催化乙烯和水的均相反应，形成乙醛。我们已经使用密度泛函理论计算方法详细研究了该反应的机理。推定的活性最高的催化剂是二聚体络合物，已通过醋酸钯配体配位的两个钯离子簇模拟。活性位点由钯离子之一形成。在乙酸钯催化的Wacker方法中，乙烯配位为钯。接下来，在外球机理中与溶液中的羟基物质偶联。一系列的氢转移（其中乙酸末端酯参与）将羟乙基配体转化为乙醛。最后，产物解吸。总体反应焓是放热的。速率确定步骤是氢转移的一种，它是导致乙醛形成的步骤。该步骤的成本为61 kJ / mol。推测所有反应都发生在配位区内，因此溶剂中的氢不会掺入产物中。在所有步骤中都明确考虑了溶剂效果。

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