How Solvent Affects C-H Activation and Hydrogen Production Pathways in Homogeneous Ru-Catalyzed Methanol Dehydrogenation Reactions.
How Solvent Affects C-H Activation and Hydrogen Production Pathways in Homogeneous Ru-Catalyzed Methanol Dehydrogenation Reactions.
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DOI：
10.1021/acscatal.8b01177
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发表时间：
2018-08-03
期刊：
影响因子：
12.9
通讯作者：
Meijer EJ
中科院分区：
文献类型：
--
作者：
Sinha V;Govindarajan N;de Bruin B;Meijer EJ
洞察甲醇脱氢催化循环的机制，由一个高活性的PNP钳形钌配合物在甲醇溶剂中催化，使用DFT为基础的分子动力学与明确的描述的溶剂，以及静态DFT计算使用微溶剂化模型。与以前的结果相反，我们发现催化剂的酰胺基部分在催化条件下被永久质子化。溶剂分子积极参与关键的反应步骤，并显着影响的反应障碍相比，纯气相模型，这是一个直接的结果，增强溶剂稳定的甲醇阴离子中间体。此外，计算表明，该系统不通过通常假设的Noyori型外层金属配体合作途径。我们的研究结果表明，将溶剂的分子描述，以获得更深入和准确的理解的反应途径的重要性，并强调需要涉及明确的溶剂分子以现实的方式模拟复杂的催化过程。
Insights into the mechanism of the catalytic cycle for methanol dehydrogenation catalyzed by a highly active PNP pincer ruthenium complex in methanol solvent are presented, using DFT-based molecular dynamics with an explicit description of the solvent, as well as static DFT calculations using microsolvation models. In contrast to previous results, we find the amido moiety of the catalyst to be permanently protonated under catalytic conditions. Solvent molecules actively participate in crucial reaction steps and significantly affect the reaction barriers when compared to pure gas-phase models, which is a direct result of the enhanced solvent stabilization of methoxide anion intermediates. Further, the calculations reveal that this system does not operate via the commonly assumed Noyori-type outer-sphere metal–ligand cooperative pathway. Our results show the importance of incorporating a molecular description of the solvent to gain a deeper and accurate understanding of the reaction pathways, and stress on the need to involve explicit solvent molecules to model complex catalytic processes in a realistic manner.
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