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How Solvent Affects C-H Activation and Hydrogen Production Pathways in Homogeneous Ru-Catalyzed Methanol Dehydrogenation Reactions.
ACS Catalysis ( IF 11.3 ) Pub Date : 2018-06-12 , DOI: 10.1021/acscatal.8b01177 Vivek Sinha 1 , Nitish Govindarajan 2 , Bas de Bruin 1 , Evert Jan Meijer 2
ACS Catalysis ( IF 11.3 ) Pub Date : 2018-06-12 , DOI: 10.1021/acscatal.8b01177 Vivek Sinha 1 , Nitish Govindarajan 2 , Bas de Bruin 1 , Evert Jan Meijer 2
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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.
中文翻译：
溶剂如何影响均相Ru催化甲醇脱氢反应中的CH活化和产氢途径。
使用基于DFT的分子动力学以及对溶剂的明确描述，以及使用微溶剂模型的静态DFT计算，对由甲醇中的高活性PNP钳形钌络合物催化的甲醇脱氢催化循环的机理进行了介绍。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。与纯气相模型相比，溶剂分子积极参与关键的反应步骤，并显着影响反应壁垒，这是甲醇盐阴离子中间体的增强溶剂稳定性的直接结果。此外，计算表明该系统不能通过通常假定的Noyori型外球金属-配体协同途径进行操作。
更新日期：2018-06-12
中文翻译：
溶剂如何影响均相Ru催化甲醇脱氢反应中的CH活化和产氢途径。
使用基于DFT的分子动力学以及对溶剂的明确描述，以及使用微溶剂模型的静态DFT计算，对由甲醇中的高活性PNP钳形钌络合物催化的甲醇脱氢催化循环的机理进行了介绍。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。与纯气相模型相比，溶剂分子积极参与关键的反应步骤，并显着影响反应壁垒，这是甲醇盐阴离子中间体的增强溶剂稳定性的直接结果。此外，计算表明该系统不能通过通常假定的Noyori型外球金属-配体协同途径进行操作。
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