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首页> 外文期刊>Chemistry: A European journal >The nature of [PdCl _2(C _2H _4)(H _2O)] as an active species in the Wacker process: New insights from Ab initio molecular dynamics simulations
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The nature of [PdCl _2(C _2H _4)(H _2O)] as an active species in the Wacker process: New insights from Ab initio molecular dynamics simulations

机译：[PdCl _2（C _2H _4）（H _2O）]在Wacker过程中作为活性物质的性质：从头算分子动力学模拟的新见解

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First-principles molecular dynamics coupled with metadynamics have been used to gain a deeper insight into the reaction mechanism of the Wacker process by determining the nature of the active species. An explicit and dynamic representation of the aqueous solvent, which was essential for modeling this reaction, was efficiently included into the simulations. Prompted by our earlier results, which showed that the configuration of the catalytically active species [PdCl _2(H _2O)(C _2H _4)] was crucial in the subsequent steps of the Wacker process, herein we focused on the preceding equilibria that led to the formation of both the cis and trans isomers. Starting from the initial catalyst, [PdCl _4] ~(2-), the free-energy barriers for the forward and backward reactions were calculated. These results confirmed the relevance of the trans intermediate in the reaction mechanism, whilst conversely, they showed that the cis configuration played no role in it. This sole participation of the trans intermediate has some very important implications; besides the mechanistic interpretation of the initial steps in the Wacker reaction mechanism, the analysis of these equilibria provides additional information about the chemical nature of these ligand-substitution processes.
机译：第一性原理分子动力学与元动力学相结合，已被用来通过确定活性物质的性质来更深入地了解瓦克过程的反应机理。有效地将水溶剂的显式和动态表示形式（对该模型进行建模至关重要）有效地包含在模拟中。我们先前的结果提示，催化活性物质[PdCl _2（H _2O）（C _2H _4）]的构型在Wacker工艺的后续步骤中至关重要，在此我们集中于导致顺式和反式异构体的形成从初始催化剂[PdCl _4]〜（2-）开始，计算了正向和反向反应的自由能垒。这些结果证实了反式中间体在反应机理中的相关性，相反，他们表明顺式构型在其中没有作用。反式中间体的这种唯一参与具有一些非常重要的意义。除了对瓦克反应机理中初始步骤的机理解释外，对这些平衡的分析还提供了有关这些配体取代过程化学性质的更多信息。

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