Adam M. Ashcraft, Shawna L. Balof, Carl A. Jones, Caleb A. Bohannon, Katherine B. McKnight, Riley C. Cork, Julia R. Cravey and Hans-Jörg Schanz*,
{"title":"利用带有 pH 响应性 N-杂环羰配体的亚烷基钌引发剂实现快速可控的水性开环偏聚作用","authors":"Adam M. Ashcraft, Shawna L. Balof, Carl A. Jones, Caleb A. Bohannon, Katherine B. McKnight, Riley C. Cork, Julia R. Cravey and Hans-Jörg Schanz*, ","doi":"10.1021/acs.organomet.4c0024110.1021/acs.organomet.4c00241","DOIUrl":null,"url":null,"abstract":"<p >A pentacoordinate ruthenium benzylidene complex was synthesized and characterized, bearing a sterically demanding NHC ligand containing two β-dimethylaminoethoxy groups, two chloride ligands, and a pH-responsive DMAP ligand. The NHC ligand requires only one additional step in the standard synthesis from commercially available precursors, which makes it a highly attractive specialized ligand for aqueous applications. The catalyst was employed in acidic aqueous media, exhibiting unprecedented high activity and efficiency in the aqueous ROMP of various water-soluble (7-oxa)norbornene derivatives. In addition to the elevated activity, the aqueous polymerization also proceeds with first-order kinetics with catalyst loadings between 0.1% and 1%, indicating the potential for controlled living ROMP. Aqueous RCM was performed with diallylammonium chloride in aqueous HCl. The metathesis reaction was active for several minutes only, but conversions into the predicted 2,5-dihydropyrrole of up to 30% were accomplished with 1% catalyst loading. Reaction times past 20 min did not afford additional RCM product. The unprecedented metathesis reactivity, in particular in aqueous ROMP, makes this catalyst the first representative of a new and highly active generation of olefin metathesis catalysts for homogeneous aqueous applications.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 6","pages":"720–728 720–728"},"PeriodicalIF":2.9000,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Fast and Controlled Aqueous Ring-Opening Metathesis Polymerization with a Ruthenium Alkylidene Initiator Bearing a pH-Responsive N-Heterocyclic Carbene Ligand\",\"authors\":\"Adam M. Ashcraft, Shawna L. Balof, Carl A. Jones, Caleb A. Bohannon, Katherine B. McKnight, Riley C. Cork, Julia R. Cravey and Hans-Jörg Schanz*, \",\"doi\":\"10.1021/acs.organomet.4c0024110.1021/acs.organomet.4c00241\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A pentacoordinate ruthenium benzylidene complex was synthesized and characterized, bearing a sterically demanding NHC ligand containing two β-dimethylaminoethoxy groups, two chloride ligands, and a pH-responsive DMAP ligand. The NHC ligand requires only one additional step in the standard synthesis from commercially available precursors, which makes it a highly attractive specialized ligand for aqueous applications. The catalyst was employed in acidic aqueous media, exhibiting unprecedented high activity and efficiency in the aqueous ROMP of various water-soluble (7-oxa)norbornene derivatives. In addition to the elevated activity, the aqueous polymerization also proceeds with first-order kinetics with catalyst loadings between 0.1% and 1%, indicating the potential for controlled living ROMP. Aqueous RCM was performed with diallylammonium chloride in aqueous HCl. The metathesis reaction was active for several minutes only, but conversions into the predicted 2,5-dihydropyrrole of up to 30% were accomplished with 1% catalyst loading. Reaction times past 20 min did not afford additional RCM product. The unprecedented metathesis reactivity, in particular in aqueous ROMP, makes this catalyst the first representative of a new and highly active generation of olefin metathesis catalysts for homogeneous aqueous applications.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"44 6\",\"pages\":\"720–728 720–728\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-03-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00241\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00241","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Fast and Controlled Aqueous Ring-Opening Metathesis Polymerization with a Ruthenium Alkylidene Initiator Bearing a pH-Responsive N-Heterocyclic Carbene Ligand
A pentacoordinate ruthenium benzylidene complex was synthesized and characterized, bearing a sterically demanding NHC ligand containing two β-dimethylaminoethoxy groups, two chloride ligands, and a pH-responsive DMAP ligand. The NHC ligand requires only one additional step in the standard synthesis from commercially available precursors, which makes it a highly attractive specialized ligand for aqueous applications. The catalyst was employed in acidic aqueous media, exhibiting unprecedented high activity and efficiency in the aqueous ROMP of various water-soluble (7-oxa)norbornene derivatives. In addition to the elevated activity, the aqueous polymerization also proceeds with first-order kinetics with catalyst loadings between 0.1% and 1%, indicating the potential for controlled living ROMP. Aqueous RCM was performed with diallylammonium chloride in aqueous HCl. The metathesis reaction was active for several minutes only, but conversions into the predicted 2,5-dihydropyrrole of up to 30% were accomplished with 1% catalyst loading. Reaction times past 20 min did not afford additional RCM product. The unprecedented metathesis reactivity, in particular in aqueous ROMP, makes this catalyst the first representative of a new and highly active generation of olefin metathesis catalysts for homogeneous aqueous applications.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.