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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Concerted or stepwise hydrogen transfer in the transfer hydrogenation of acetophenone catalyzed by ruthenium-acetamido complex: A theoretical mechanistic investigation
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Concerted or stepwise hydrogen transfer in the transfer hydrogenation of acetophenone catalyzed by ruthenium-acetamido complex: A theoretical mechanistic investigation

机译：钌-乙酰氨基配合物催化苯乙酮转移加氢中的协同或逐步氢转移：理论机理研究

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摘要

In this paper, the mechanism of transfer hydrogenation of acetophenone catalyzed by ruthenium-acetamido complex was studied using density function theory (DFT) method. The catalytic cycle of transfer hydrogenation consists of hydrogen transfer (HT) step and dehydrogenation (DH) step of isopropanol (IPA). Inner sphere mechanism (paths 1 and 7) and outer sphere mechanism (paths 2-6) in HT step are fully investigated. Calculated results indicate that DH step of IPA (from ~i1 to ~i2) is the rate-determining step in the whole catalytic cycle, which has a potential energy barrier of 16.2 kcal/mol. On the other hand, the maximum potential energy barriers of paths 1-7 in the HT step are 5.9, 12.7, 24.4, 16.8, 23.7, 7.2, and 6.1 kcal/mol, respectively. The inner sphere pathways (paths 1 and 7) are favorable hydrogen transfer modes compared with outer sphere pathways, and the proton transferred to the oxygen atom of acetophenone comes from the hydroxyl group but not from amino group of acetamido ligand. Those theoretical results are in agreement with experimental report. However, in view of this DFT study in the inner sphere mechanism of HT step, hydride transfer and proton transfer are concerted and asynchronous hydrogen transfer but not a stepwise one, and hydride transfer precedes proton transfer in this case.
机译：本文利用密度泛函理论（DFT）方法研究了钌-乙酰氨基配合物催化苯乙酮转移加氢的机理。转移氢化的催化循环由异丙醇（IPA）的氢转移（HT）步骤和脱氢（DH）步骤组成。充分研究了HT步骤中的内球机理（路径1和7）和外球机理（路径2-6）。计算结果表明，IPA的DH步骤（从〜i1到〜i2）是整个催化循环中的速率决定步骤，其势垒为16.2 kcal / mol。另一方面，HT步骤中路径1-7的最大势能垒分别为5.9、12.7、24.4、16.8、23.7、7.2和6.1 kcal / mol。与外球途径相比，内球途径（途径1和7）是有利的氢转移方式，转移到苯乙酮氧原子上的质子来自羟基，而不是来自乙酰氨基配体的氨基。这些理论结果与实验报告一致。然而，鉴于在HT步的内球机理中进行的DFT研究，氢化物转移和质子转移是协调一致的，而异步氢转移不是逐步的，氢转移在这种情况下先于质子转移。

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