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
{"title":"带有 N-杂环碳配体的钌(II)络合物催化的己烯氢化反应","authors":"Sofiene Achour,&nbsp;Zied Hosni,&nbsp;Bahoueddine Tangour","doi":"10.1002/qua.27456","DOIUrl":null,"url":null,"abstract":"<p>In this study, we investigated the mechanism of the inactivated hexene hydrogenation reaction catalyzed by a ruthenium (II) complex containing “<i>N</i>-heterocyclic carbene” (NHC) ligands, specifically SIMes and CBA, using DFT calculations. Our focus was on RuH(OSO<sub>2</sub>CF<sub>3</sub>)(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<sup>−1</sup>. 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 <i>π</i> to <i>σ</i> 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 H<sub>2</sub> 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<sup>−1</sup>. 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<sup>−1</sup>, providing notable benefits.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3000,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.27456","citationCount":"0","resultStr":"{\"title\":\"Hydrogenation of hexene catalyzed by a ruthenium (II) complex with N-heterocyclic carbene ligands\",\"authors\":\"Sofiene Achour,&nbsp;Zied Hosni,&nbsp;Bahoueddine Tangour\",\"doi\":\"10.1002/qua.27456\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>In this study, we investigated the mechanism of the inactivated hexene hydrogenation reaction catalyzed by a ruthenium (II) complex containing “<i>N</i>-heterocyclic carbene” (NHC) ligands, specifically SIMes and CBA, using DFT calculations. Our focus was on RuH(OSO<sub>2</sub>CF<sub>3</sub>)(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<sup>−1</sup>. 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 <i>π</i> to <i>σ</i> 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 H<sub>2</sub> 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<sup>−1</sup>. 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<sup>−1</sup>, providing notable benefits.</p>\",\"PeriodicalId\":182,\"journal\":{\"name\":\"International Journal of Quantum Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2024-07-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.27456\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"International Journal of Quantum Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/qua.27456\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Quantum Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/qua.27456","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
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。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

摘要图片

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
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.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
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.
期刊最新文献
Exploring Chlorinated Solvents as Electrolytes for Lithium Metal Batteries: A DFT and MD Study Dihydro-1H-Pyrazoles as Donor Blocks in Donor–Acceptor Chromophores for Electro-Optics: A DFT Study of Hyperpolaizability and Electronic Excitations Evaluating Electronic Properties of Self-Assembled Indium Phosphide Nanomaterials as High-Efficient Solar Cell Generation of Database of Polymer Acceptors and Machine Learning-Assisted Screening of Efficient Candidates DFT Computation, Spectroscopic, Hirshfeld Surface, Docking and Topological Analysis on 2,2,5-Trimethyl-1,3-Dioxane-5-Carboxylic Acid as Potent Anti-Cancer Agent
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1