Patrick Probst, Moritz Lindemann, Johanna R. Bruckner, Boshra Atwi, Dongren Wang, Felix R. Fischer, Marc Högler, Matthias Bauer, Niels Hansen, Michael Dyballa and Michael R. Buchmeiser*,
{"title":"约束下的环膨胀复分解聚合","authors":"Patrick Probst, Moritz Lindemann, Johanna R. Bruckner, Boshra Atwi, Dongren Wang, Felix R. Fischer, Marc Högler, Matthias Bauer, Niels Hansen, Michael Dyballa and Michael R. Buchmeiser*, ","doi":"10.1021/jacs.4c1817110.1021/jacs.4c18171","DOIUrl":null,"url":null,"abstract":"<p >The cationic molybdenum alkylidyne <i>N</i>-heterocyclic carbene (NHC) complex [Mo(C-<i>p</i>-OMeC<sub>6</sub>H<sub>4</sub>)(OCMe(CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub> (IMes)][B(Ar<sup>F</sup><sub>4</sub>] (IMes = 1,3-dimesitylimidazol-2-ylidene) was selectively immobilized inside the pores of ordered mesoporous silica (OMS) with pore diameters of 66, 56, and 28 Å and used in the ring-expansion metathesis polymerization (REMP) of cyclic olefins to yield cyclic polymers. A strong confinement effect was observed for <i>cis</i>-cyclooctene (<i>c</i>COE), 1,5-cyclooctadiene (COD), (+)-2,3-<i>endo,exo</i>-dicarbomethoxynorborn-5-ene ((+)-DCMNBE), and 2-methyl-2-phenylcycloprop-1-ene (MPCP), allowing for the synthesis of low-molecular-weight cyclic polymers even at a high monomer concentration. The exclusive formation of cyclic polymers was demonstrated by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry. Confinement also influences stereoselectivity, resulting in a pronounced increase in Z-selectivity and in an increased <i>cis</i>-syndiospecificity.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 10","pages":"8741–8750 8741–8750"},"PeriodicalIF":15.6000,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ring-Expansion Metathesis Polymerization under Confinement\",\"authors\":\"Patrick Probst, Moritz Lindemann, Johanna R. Bruckner, Boshra Atwi, Dongren Wang, Felix R. Fischer, Marc Högler, Matthias Bauer, Niels Hansen, Michael Dyballa and Michael R. Buchmeiser*, \",\"doi\":\"10.1021/jacs.4c1817110.1021/jacs.4c18171\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The cationic molybdenum alkylidyne <i>N</i>-heterocyclic carbene (NHC) complex [Mo(C-<i>p</i>-OMeC<sub>6</sub>H<sub>4</sub>)(OCMe(CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub> (IMes)][B(Ar<sup>F</sup><sub>4</sub>] (IMes = 1,3-dimesitylimidazol-2-ylidene) was selectively immobilized inside the pores of ordered mesoporous silica (OMS) with pore diameters of 66, 56, and 28 Å and used in the ring-expansion metathesis polymerization (REMP) of cyclic olefins to yield cyclic polymers. A strong confinement effect was observed for <i>cis</i>-cyclooctene (<i>c</i>COE), 1,5-cyclooctadiene (COD), (+)-2,3-<i>endo,exo</i>-dicarbomethoxynorborn-5-ene ((+)-DCMNBE), and 2-methyl-2-phenylcycloprop-1-ene (MPCP), allowing for the synthesis of low-molecular-weight cyclic polymers even at a high monomer concentration. The exclusive formation of cyclic polymers was demonstrated by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry. Confinement also influences stereoselectivity, resulting in a pronounced increase in Z-selectivity and in an increased <i>cis</i>-syndiospecificity.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"147 10\",\"pages\":\"8741–8750 8741–8750\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2025-02-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.4c18171\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c18171","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Ring-Expansion Metathesis Polymerization under Confinement
The cationic molybdenum alkylidyne N-heterocyclic carbene (NHC) complex [Mo(C-p-OMeC6H4)(OCMe(CF3)2)2 (IMes)][B(ArF4] (IMes = 1,3-dimesitylimidazol-2-ylidene) was selectively immobilized inside the pores of ordered mesoporous silica (OMS) with pore diameters of 66, 56, and 28 Å and used in the ring-expansion metathesis polymerization (REMP) of cyclic olefins to yield cyclic polymers. A strong confinement effect was observed for cis-cyclooctene (cCOE), 1,5-cyclooctadiene (COD), (+)-2,3-endo,exo-dicarbomethoxynorborn-5-ene ((+)-DCMNBE), and 2-methyl-2-phenylcycloprop-1-ene (MPCP), allowing for the synthesis of low-molecular-weight cyclic polymers even at a high monomer concentration. The exclusive formation of cyclic polymers was demonstrated by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry. Confinement also influences stereoselectivity, resulting in a pronounced increase in Z-selectivity and in an increased cis-syndiospecificity.
期刊介绍：
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
