关于受挫路易斯对催化的杂环烯 C-H 活化的密度泛函理论研究:电子效应对机理变化的调整

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Journal of Physical Organic Chemistry Pub Date : 2024-07-22 DOI:10.1002/poc.4652
Youxiang Shao, Kang Xiao, Huize Wang, Yalan Liu
{"title":"关于受挫路易斯对催化的杂环烯 C-H 活化的密度泛函理论研究:电子效应对机理变化的调整","authors":"Youxiang Shao,&nbsp;Kang Xiao,&nbsp;Huize Wang,&nbsp;Yalan Liu","doi":"10.1002/poc.4652","DOIUrl":null,"url":null,"abstract":"<p>Unreactive C-H bond activation is a new horizon for frustrated Lewis pairs (FLPs) chemistry. Although concerted mechanism (Science 2015, 349, 513) and stepwise carbene mechanism (Org. Lett. 2018, 20, 1102) have been proposed for the FLPs catalyzed C-H bond activation of 1-methylpyrrole, the influence of electronic properties of FLPs on the reaction mechanism is far away from well-understood. In this study, an assortment of P-B type FLPs with different electronic characteristic was employed to study the catalyzed C-H bond activation of 1-methylpyrrole by using density functional theory calculations. Detailed calculations demonstrated that the reactivity variation and the reaction mechanism binary of FLPs catalyzed C-H activation can be varied by tuning electronic effect of Lewis base center. On the one hand, the concerted C-H activation reactivity is mainly controlled by the electron donation of the lone pair of Lewis base center; thus, the FLPs with electron-donating substituents <b>(FLP1</b>, <b>FLP2</b>, and <b>FLP3)</b> catalyzed the C-H bond activation through concerted mechanism. On the other hand, the reactivity of stepwise carbene mechanism is mostly attributed to the vacant orbital of Lewis acid center; as a result, the <b>FLP5</b> bearing -P(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub> preferred to catalyzed the bond activation through concerted mechanism. In contrast, a metathesis mechanism through strained four-membered ring transition state is less feasible. These results should provide deeper insight and broader perspective to understand the structure and function of FLPs for rational design of FLPs catalyzed C-H bond activation.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Density functional theory study on frustrated Lewis pairs catalyzed C-H activation of heteroarenes: Mechanism variation tuning by electronic effect\",\"authors\":\"Youxiang Shao,&nbsp;Kang Xiao,&nbsp;Huize Wang,&nbsp;Yalan Liu\",\"doi\":\"10.1002/poc.4652\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Unreactive C-H bond activation is a new horizon for frustrated Lewis pairs (FLPs) chemistry. Although concerted mechanism (Science 2015, 349, 513) and stepwise carbene mechanism (Org. Lett. 2018, 20, 1102) have been proposed for the FLPs catalyzed C-H bond activation of 1-methylpyrrole, the influence of electronic properties of FLPs on the reaction mechanism is far away from well-understood. In this study, an assortment of P-B type FLPs with different electronic characteristic was employed to study the catalyzed C-H bond activation of 1-methylpyrrole by using density functional theory calculations. Detailed calculations demonstrated that the reactivity variation and the reaction mechanism binary of FLPs catalyzed C-H activation can be varied by tuning electronic effect of Lewis base center. On the one hand, the concerted C-H activation reactivity is mainly controlled by the electron donation of the lone pair of Lewis base center; thus, the FLPs with electron-donating substituents <b>(FLP1</b>, <b>FLP2</b>, and <b>FLP3)</b> catalyzed the C-H bond activation through concerted mechanism. On the other hand, the reactivity of stepwise carbene mechanism is mostly attributed to the vacant orbital of Lewis acid center; as a result, the <b>FLP5</b> bearing -P(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub> preferred to catalyzed the bond activation through concerted mechanism. In contrast, a metathesis mechanism through strained four-membered ring transition state is less feasible. These results should provide deeper insight and broader perspective to understand the structure and function of FLPs for rational design of FLPs catalyzed C-H bond activation.</p>\",\"PeriodicalId\":16829,\"journal\":{\"name\":\"Journal of Physical Organic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2024-07-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Physical Organic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/poc.4652\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Physical Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/poc.4652","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0

摘要

非反应性 C-H 键活化是受挫路易斯对(FLPs)化学的一个新视野。虽然已有人提出了FLPs催化1-甲基吡咯C-H键活化的协同机理(Science 2015, 349, 513)和逐步碳化机理(Org. Lett.本研究采用密度泛函理论计算方法,研究了多种具有不同电子特性的 P-B 型 FLPs 催化 1-甲基吡咯的 C-H 键活化反应。详细的计算结果表明,FLPs 催化 C-H 活化的反应活性变化和反应机理二元化可以通过调整路易斯碱中心的电子效应来实现。一方面,协同 C-H 活化反应活性主要受路易斯碱中心孤对电子捐献的控制;因此,具有电子捐献取代基的 FLPs(FLP1、FLP2 和 FLP3)通过协同机制催化 C-H 键活化。另一方面,逐步碳化机制的反应活性主要归因于路易斯酸中心的空闲轨道,因此,带有 -P(C6F5)2 的 FLP5 更倾向于通过协同机制催化键的活化。相比之下,通过应变四元环过渡态的偏合成机制则不太可行。这些结果将为我们深入了解 FLPs 的结构和功能,合理设计 FLPs 催化 C-H 键活化提供更广阔的视角。
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
Density functional theory study on frustrated Lewis pairs catalyzed C-H activation of heteroarenes: Mechanism variation tuning by electronic effect

Unreactive C-H bond activation is a new horizon for frustrated Lewis pairs (FLPs) chemistry. Although concerted mechanism (Science 2015, 349, 513) and stepwise carbene mechanism (Org. Lett. 2018, 20, 1102) have been proposed for the FLPs catalyzed C-H bond activation of 1-methylpyrrole, the influence of electronic properties of FLPs on the reaction mechanism is far away from well-understood. In this study, an assortment of P-B type FLPs with different electronic characteristic was employed to study the catalyzed C-H bond activation of 1-methylpyrrole by using density functional theory calculations. Detailed calculations demonstrated that the reactivity variation and the reaction mechanism binary of FLPs catalyzed C-H activation can be varied by tuning electronic effect of Lewis base center. On the one hand, the concerted C-H activation reactivity is mainly controlled by the electron donation of the lone pair of Lewis base center; thus, the FLPs with electron-donating substituents (FLP1, FLP2, and FLP3) catalyzed the C-H bond activation through concerted mechanism. On the other hand, the reactivity of stepwise carbene mechanism is mostly attributed to the vacant orbital of Lewis acid center; as a result, the FLP5 bearing -P(C6F5)2 preferred to catalyzed the bond activation through concerted mechanism. In contrast, a metathesis mechanism through strained four-membered ring transition state is less feasible. These results should provide deeper insight and broader perspective to understand the structure and function of FLPs for rational design of FLPs catalyzed C-H bond activation.

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
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
期刊最新文献
Issue Information Cover Image Cover Image Issue Information Enhanced Hyperpolarizabilities Through p‐Phenylene Bridges: Computational Studies on Metamerism and Functional Molecular Properties of Pyridinium–Dicyanomethanide‐Based Zwitterions
×
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