自加速扩环复分解聚合

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-03-11 DOI:10.1021/acscatal.5c01208

Courtney M. Sever, Alec M. Esper, Ion Ghiviriga, Daniel W. Lester, Arkadios Marathianos, Christian Ehm, Adam S. Veige

{"title":"自加速扩环复分解聚合","authors":"Courtney M. Sever, Alec M. Esper, Ion Ghiviriga, Daniel W. Lester, Arkadios Marathianos, Christian Ehm, Adam S. Veige","doi":"10.1021/acscatal.5c01208","DOIUrl":null,"url":null,"abstract":"We report the one-step synthesis of a double-tethered metallacyclobutane molybdenum catalyst for ring expansion metathesis polymerization, a method increasingly popular for cyclic polymer production. The metallacyclobutane’s geometry, based on 13C NMR and DFT analysis, suggests it should not participate in metathesis. However, polymerization of norbornene showed high activity (an upper limit of 1,000,000,000 gpolymer molcat–1 h–1). DFT studies reveal that the catalyst’s slow initiation and fast propagation arise from a self-accelerating effect triggered by increasing steric demand, causing a geometry shift from square-pyramidal to trigonal bipyramidal. This insight will advance catalyst design principles and, in the future, allow for more precise control of the molecular weight, dispersity, and tacticity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"5 1","pages":""},"PeriodicalIF":13.1000,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Self-Accelerating Ring Expansion Metathesis Polymerization\",\"authors\":\"Courtney M. Sever, Alec M. Esper, Ion Ghiviriga, Daniel W. Lester, Arkadios Marathianos, Christian Ehm, Adam S. Veige\",\"doi\":\"10.1021/acscatal.5c01208\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"We report the one-step synthesis of a double-tethered metallacyclobutane molybdenum catalyst for ring expansion metathesis polymerization, a method increasingly popular for cyclic polymer production. The metallacyclobutane’s geometry, based on 13C NMR and DFT analysis, suggests it should not participate in metathesis. However, polymerization of norbornene showed high activity (an upper limit of 1,000,000,000 gpolymer molcat–1 h–1). DFT studies reveal that the catalyst’s slow initiation and fast propagation arise from a self-accelerating effect triggered by increasing steric demand, causing a geometry shift from square-pyramidal to trigonal bipyramidal. This insight will advance catalyst design principles and, in the future, allow for more precise control of the molecular weight, dispersity, and tacticity.\",\"PeriodicalId\":9,\"journal\":{\"name\":\"ACS Catalysis \",\"volume\":\"5 1\",\"pages\":\"\"},\"PeriodicalIF\":13.1000,\"publicationDate\":\"2025-03-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Catalysis \",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acscatal.5c01208\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.5c01208","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

摘要

我们报道了一种用于环扩张复分解聚合的双系链金属环丁烷钼催化剂的一步合成，这是一种日益流行的环状聚合物生产方法。金属环丁烷的几何结构，基于13C核磁共振和DFT分析，表明它不应该参与复分解。然而，降冰片烯的聚合表现出较高的活性（上限为1,000,000,000 gpolymer molcat-1 h-1）。DFT研究表明，催化剂的缓慢起始和快速传播是由空间需求增加引发的自加速效应引起的，导致几何结构从正方形锥体转变为三角形双锥体。这一见解将推进催化剂设计原则，并在未来允许更精确地控制分子量，分散性和战术。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Self-Accelerating Ring Expansion Metathesis Polymerization

查看原文本刊更多论文

Self-Accelerating Ring Expansion Metathesis Polymerization

We report the one-step synthesis of a double-tethered metallacyclobutane molybdenum catalyst for ring expansion metathesis polymerization, a method increasingly popular for cyclic polymer production. The metallacyclobutane’s geometry, based on ¹³C NMR and DFT analysis, suggests it should not participate in metathesis. However, polymerization of norbornene showed high activity (an upper limit of 1,000,000,000 g_polymer mol_cat^–1 h^–1). DFT studies reveal that the catalyst’s slow initiation and fast propagation arise from a self-accelerating effect triggered by increasing steric demand, causing a geometry shift from square-pyramidal to trigonal bipyramidal. This insight will advance catalyst design principles and, in the future, allow for more precise control of the molecular weight, dispersity, and tacticity.

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

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.