Amrutha Kizhuvedath, Jose John Mallikasseri, Jomon Mathew
{"title":"揭示环三苯乙烯的反应途径:计算分析","authors":"Amrutha Kizhuvedath, Jose John Mallikasseri, Jomon Mathew","doi":"10.1007/s00214-024-03099-9","DOIUrl":null,"url":null,"abstract":"<p>Cyclotrisilenes can pursue four types of reaction pathways with unsaturated substrates: <i>π</i>-addition, <i>σ</i>-insertion, exocyclic <i>σ</i>-insertion, and ring-opening reactions. A computational investigation of all these reaction pathways of 1,2,3,3-tetramethyl cyclotrisilene c-Si<sub>3</sub>Me<sub>4</sub> (<b>I</b>) and 1,2-bis(trimethylsilyl)-3,3-dimethyl cyclotrisilene c-Si<sub>3</sub>Me<sub>2</sub>(SiMe<sub>3</sub>)<sub>2</sub> (<b>II</b>) with phenylacetylene (<b>R1</b>) and benzaldehyde (<b>R2</b>) is carried out. The reaction pathways are found to be significantly influenced by the substituents attached to the cyclotrisilene ring. Both the <i>π</i>-addition and the <i>σ</i>-insertion reactions proceed with moderate activation energy and high exoergicity, and the electronic nature of the functional group is crucial in deciding the favorable pathway. The exocyclic <i>σ</i>-insertion reactions are found to possess a huge energy barrier, irrespective of the steric and electronic nature of cyclotrisilenes and the substrates. While the course of the reaction and the viability of the ring-opening reaction with phenylacetylene are impacted by the nature of cyclotrisilene, the ring-opening reactions of <b>I</b> and <b>II</b> with benzaldehyde are both highly endoergic.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"30 1","pages":""},"PeriodicalIF":1.6000,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unraveling the reaction pathways of cyclotrisilenes: a computational analysis\",\"authors\":\"Amrutha Kizhuvedath, Jose John Mallikasseri, Jomon Mathew\",\"doi\":\"10.1007/s00214-024-03099-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Cyclotrisilenes can pursue four types of reaction pathways with unsaturated substrates: <i>π</i>-addition, <i>σ</i>-insertion, exocyclic <i>σ</i>-insertion, and ring-opening reactions. A computational investigation of all these reaction pathways of 1,2,3,3-tetramethyl cyclotrisilene c-Si<sub>3</sub>Me<sub>4</sub> (<b>I</b>) and 1,2-bis(trimethylsilyl)-3,3-dimethyl cyclotrisilene c-Si<sub>3</sub>Me<sub>2</sub>(SiMe<sub>3</sub>)<sub>2</sub> (<b>II</b>) with phenylacetylene (<b>R1</b>) and benzaldehyde (<b>R2</b>) is carried out. The reaction pathways are found to be significantly influenced by the substituents attached to the cyclotrisilene ring. Both the <i>π</i>-addition and the <i>σ</i>-insertion reactions proceed with moderate activation energy and high exoergicity, and the electronic nature of the functional group is crucial in deciding the favorable pathway. The exocyclic <i>σ</i>-insertion reactions are found to possess a huge energy barrier, irrespective of the steric and electronic nature of cyclotrisilenes and the substrates. While the course of the reaction and the viability of the ring-opening reaction with phenylacetylene are impacted by the nature of cyclotrisilene, the ring-opening reactions of <b>I</b> and <b>II</b> with benzaldehyde are both highly endoergic.</p>\",\"PeriodicalId\":23045,\"journal\":{\"name\":\"Theoretical Chemistry Accounts\",\"volume\":\"30 1\",\"pages\":\"\"},\"PeriodicalIF\":1.6000,\"publicationDate\":\"2024-03-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Theoretical Chemistry Accounts\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1007/s00214-024-03099-9\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Theoretical Chemistry Accounts","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s00214-024-03099-9","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
环三苯乙烯可以与不饱和底物进行四种类型的反应途径:π-加成、σ-插入、外环σ-插入和开环反应。对 1,2,3,3-四甲基环三硅烯 c-Si3Me4 (I) 和 1,2-双(三甲基硅基)-3,3-二甲基环三硅烯 c-Si3Me2(SiMe3)2 (II) 与苯乙炔 (R1) 和苯甲醛 (R2) 的所有这些反应途径进行了计算研究。研究发现,环三苯乙烯环上的取代基对反应途径有很大影响。π-加成反应和σ-插入反应都以中等活化能和较高的外能进行,而官能团的电子性质是决定有利反应途径的关键。研究发现,无论环三苯乙烯和底物的立体和电子性质如何,外环σ插入反应都具有巨大的能障。虽然与苯乙炔的开环反应的过程和可行性受到环三苯乙烯性质的影响,但 I 和 II 与苯甲醛的开环反应都具有很高的内能。
Unraveling the reaction pathways of cyclotrisilenes: a computational analysis
Cyclotrisilenes can pursue four types of reaction pathways with unsaturated substrates: π-addition, σ-insertion, exocyclic σ-insertion, and ring-opening reactions. A computational investigation of all these reaction pathways of 1,2,3,3-tetramethyl cyclotrisilene c-Si3Me4 (I) and 1,2-bis(trimethylsilyl)-3,3-dimethyl cyclotrisilene c-Si3Me2(SiMe3)2 (II) with phenylacetylene (R1) and benzaldehyde (R2) is carried out. The reaction pathways are found to be significantly influenced by the substituents attached to the cyclotrisilene ring. Both the π-addition and the σ-insertion reactions proceed with moderate activation energy and high exoergicity, and the electronic nature of the functional group is crucial in deciding the favorable pathway. The exocyclic σ-insertion reactions are found to possess a huge energy barrier, irrespective of the steric and electronic nature of cyclotrisilenes and the substrates. While the course of the reaction and the viability of the ring-opening reaction with phenylacetylene are impacted by the nature of cyclotrisilene, the ring-opening reactions of I and II with benzaldehyde are both highly endoergic.
期刊介绍:
TCA publishes papers in all fields of theoretical chemistry, computational chemistry, and modeling. Fundamental studies as well as applications are included in the scope. In many cases, theorists and computational chemists have special concerns which reach either across the vertical borders of the special disciplines in chemistry or else across the horizontal borders of structure, spectra, synthesis, and dynamics. TCA is especially interested in papers that impact upon multiple chemical disciplines.