揭示在铂和铂钒团簇存在下甲酰胺加氢反应的最小能量途径:量子化学DFT/轻推弹性带研究

Natalia S. Panina, Ilya N. Klyukin, Tatyana M. Buslaeva, Andrei I. Fischer
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引用次数: 0

摘要

对铂和铂钒团簇催化反应的阶段进行了详细的研究。利用NEB功能和优化结构,通过DFT/PBE0/def2tzvp方法构建了反应的最小能量路径(MEP),并计算了最小和过渡态点。在H2的作用下,甲酰胺转化为甲胺的两步法被认为是一个试验反应。这个反应的能垒,以前没有在文献中描述过,已经被评估过了。研究表明,试剂结构特征的主要变化,以及单个H原子从团簇的一个金属中心迁移到另一个金属中心或迁移到有机底物,是在分子水平上由与过渡态系统正常振动向量相对应的位移引起的。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Revealing the Minimum Energy Pathways for Formamide Hydrogenation Reactions in the Presence of Platinum and Platinum–Vanadium Clusters: A Quantum Chemical DFT/Nudged Elastic Band Study
A detailed study on the stages of catalytic reactions involving platinum and platinum-vanadium clusters has been carried out. Minimum energy pathways (MEP) of reactions have been constructed via the DFT/PBE0/def2tzvp method using NEB functional and optimized structures, and points of minima and transition states have been calculated. A two-step process for the conversion of formamide to methylamine under the action of H2 has been considered as a test reaction. The energy barriers of this reaction, not previously described in the literature, have been evaluated. It has been shown that the main changes in the structural characteristics of the reagents, as well as the migration of single H atoms from one metal center of clusters to another or to an organic substrate, are initiated at the molecular level by shifts corresponding to the vectors of normal vibrations of systems in transition states.
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