带有 N-杂环碳配体的钌(II)络合物催化的己烯氢化反应

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL International Journal of Quantum Chemistry Pub Date : 2024-07-23 DOI:10.1002/qua.27456
Sofiene Achour, Zied Hosni, Bahoueddine Tangour
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引用次数: 0

摘要

在本研究中,我们利用 DFT 计算研究了含有 "N-杂环碳烯"(NHC)配体(特别是 SIMes 和 CBA)的钌 (II) 复合物催化失活己烯加氢反应的机理。我们的重点是 RuH(OSO2CF3)(CO)(SIMes)(CBA),它表现出卓越的催化性能。我们测试了 B3LYP-D3、cam-B3LYP 和 TPSSh 函数。由于相关的解离能较低,氢化反应是由 SIMes 而不是 CBA 的释放引发的。我们的研究结果表明,反应机制由两个连续步骤组成,每个步骤涉及一个氢原子迁移。第一步被视为动力学限制过渡态,其吉布斯自由活化势垒为 12.9 kcal mol-1。这一步涉及两个异步过程。第一个过程是氢化钌迁移到烯烃官能团的内部碳,从 π 配位模式过渡到 σ 配位模式,从而促进钌与末端烯烃碳之间形成键。第二个过程涉及钌从 Ru(II) 氧化成 Ru(IV)。这种氧化作用至关重要,因为它能使 H2 分子分解成与钌原子结合的两个氢原子。利用 RIRC 技术确定了隐藏反应中间体 Ru(II) 复合物的几何结构和第二个过程的准转变状态。第二步需要将 Ru(IV) 复合物新形成的氢化物之一迁移到末端烯烃碳上,从而释放出正己烷,其弱活化吉布斯自由能为 0.8 kcal mol-1。最后,考虑到 PCM 模型,我们探索了使用二氯甲烷作为溶剂。溶剂的存在大大降低了 SIMes 的解离能,从 17.9 kcal mol-1 降至 9.0 kcal mol-1,带来了显著的益处。
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Hydrogenation of hexene catalyzed by a ruthenium (II) complex with N-heterocyclic carbene ligands

In this study, we investigated the mechanism of the inactivated hexene hydrogenation reaction catalyzed by a ruthenium (II) complex containing “N-heterocyclic carbene” (NHC) ligands, specifically SIMes and CBA, using DFT calculations. Our focus was on RuH(OSO2CF3)(CO)(SIMes)(CBA), which exhibits excellent catalytic behavior. We tested the B3LYP-D3, cam-B3LYP, and TPSSh functionals. The hydrogenation reaction is initiated by the release of SIMes rather than CBA due to the lower associated dissociation energy. Our findings indicate a reaction mechanism consisting of two consecutive steps, each involving one hydrogen atom migration. The first step, considered as the kinetically limiting transition state, exhibits a Gibbs free activation barrier of 12.9 kcal mol−1. This step involves two asynchronous processes. The first one describes the migration of the ruthenium hydride to the internal carbon of the olefine function, transitioning from π to σ coordination mode, which promotes the formation of a bond between ruthenium and the terminal olefinic carbon. The second process involves the oxidation of ruthenium from Ru(II) to Ru(IV). This oxidation is crucial as it enables the decomposition of the H2 molecule into two hydrogen atoms bonded to the ruthenium atom. The geometrical structures of the Hidden Reaction Intermediate Ru(II) complex and the quasi-transition state of the second process have been determined by means of the RIRC technique. The second step entails the migration of one of the newly formed hydrides of the Ru(IV) complex to the terminal olefinic carbon, resulting in the release of hexane with a weak activation Gibbs free energy of .8 kcal mol−1. Lastly, we explored the use of dichloromethane as a solvent, considering the PCM model. The presence of the solvent significantly decreases the energy dissociation of SIMes from 17.9 to 9.0 kcal mol−1, providing notable benefits.

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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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