Unraveling the reaction pathways of cyclotrisilenes: a computational analysis

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Accounts of Chemical Research Pub Date : 2024-03-01 DOI:10.1007/s00214-024-03099-9
Amrutha Kizhuvedath, Jose John Mallikasseri, Jomon Mathew
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Abstract

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.

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揭示环三苯乙烯的反应途径:计算分析
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。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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