{"title":"Theoretical studies on the mechanism of Rh−catalyzed [3+2+1] cycloaddition reaction of vinylidene cyclopropane with carbon monoxide","authors":"Huimin Xu, Tao Wang, Wanjun Zhao, Ying Ren, Jianfeng Jia, Hai-Shun Wu","doi":"10.1016/j.jorganchem.2024.123487","DOIUrl":null,"url":null,"abstract":"<div><div>DFT calculations have been carried out to study the mechanism of the Rh-catalyzed Pauson-Khand [3+2+1] cycloaddition reaction of vinylidene cyclopropane with carbon monoxide, as well as the diastereoselectivity of the products. It is found that reaction initializes by oxidative addition involves the distal C−C bond cleavage of cyclopropane groups, which is promoted by Rh(I) complex, to give <em>η</em><sup>4</sup>-TMM Rh(III) intermediate, followed by CO insertion. Continuing with the next process, olefin insertion, determines the formation of the <em>cis</em>-product or <em>trans</em>-product, depending on the orientation of coordinated olefin moiety to the Rh center. The calculations provide a successful interpretation of the experimental observersed diastereoselectivity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123487"},"PeriodicalIF":2.1000,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X24004820","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/12/19 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
DFT calculations have been carried out to study the mechanism of the Rh-catalyzed Pauson-Khand [3+2+1] cycloaddition reaction of vinylidene cyclopropane with carbon monoxide, as well as the diastereoselectivity of the products. It is found that reaction initializes by oxidative addition involves the distal C−C bond cleavage of cyclopropane groups, which is promoted by Rh(I) complex, to give η4-TMM Rh(III) intermediate, followed by CO insertion. Continuing with the next process, olefin insertion, determines the formation of the cis-product or trans-product, depending on the orientation of coordinated olefin moiety to the Rh center. The calculations provide a successful interpretation of the experimental observersed diastereoselectivity.
期刊介绍：
The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds.
Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome.
The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.
京公网安备 11010802042870号
京ICP备2023020795号-1
分享
求助内容：
应助结果提醒方式：
扫码关注我们
