{"title":"含β-硫代酮酸盐和β-酮酸盐的铝配合物对ε-己内酯开环聚合反应性的影响","authors":"Prasanna Kumar Ganta, Mallemadugula Ravi Teja, Rajiv Kamaraj, Ya-Rong Tsai, Yu-Ting Chu, Anandan Sambandam, Yi-Chun Lai, Shangwu Ding and Hsuan-Ying Chen*, ","doi":"10.1021/acs.organomet.3c00383","DOIUrl":null,"url":null,"abstract":"<p >In this study, a series of Al complexes bearing β-ketiminates and β-thioketiminates were synthesized and used as catalysts in ε-caprolactone (CL) polymerization. <b>S</b><sup><b>Pr</b></sup><b>–Al</b> had the highest catalytic activity among all Al complexes bearing β-thioketiminates and was more active than <b>O</b><sup><b>Pr</b></sup><b>–Al</b> (2.8 times as high for CL polymerization) ([CL]/[<b>S</b><sup><b>Pr</b></sup><b>–Al</b>]/[BnOH] = 100:1:2, [<b>S</b><sup><b>Pr</b></sup><b>–Al</b>] = 0.02 M, conversion = 96% after 20 min at 25 °C). All Al complexes bearing β-thioketiminates exhibited higher catalytic activity (2.1- to 24.9-fold) relative to β-ketiminates. The polymerization results demonstrated that swapping oxygen atoms for sulfur atoms in β-ketiminate-associated Al complexes improved the catalytic activity of Al complexes for CL ROP.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"42 23","pages":"3405–3417"},"PeriodicalIF":2.9000,"publicationDate":"2023-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Effects of Aluminum Complexes Bearing β-Thioketiminate and β-Ketiminates on ε-Caprolactone Ring-Opening Polymerization Reactivity\",\"authors\":\"Prasanna Kumar Ganta, Mallemadugula Ravi Teja, Rajiv Kamaraj, Ya-Rong Tsai, Yu-Ting Chu, Anandan Sambandam, Yi-Chun Lai, Shangwu Ding and Hsuan-Ying Chen*, \",\"doi\":\"10.1021/acs.organomet.3c00383\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In this study, a series of Al complexes bearing β-ketiminates and β-thioketiminates were synthesized and used as catalysts in ε-caprolactone (CL) polymerization. <b>S</b><sup><b>Pr</b></sup><b>–Al</b> had the highest catalytic activity among all Al complexes bearing β-thioketiminates and was more active than <b>O</b><sup><b>Pr</b></sup><b>–Al</b> (2.8 times as high for CL polymerization) ([CL]/[<b>S</b><sup><b>Pr</b></sup><b>–Al</b>]/[BnOH] = 100:1:2, [<b>S</b><sup><b>Pr</b></sup><b>–Al</b>] = 0.02 M, conversion = 96% after 20 min at 25 °C). All Al complexes bearing β-thioketiminates exhibited higher catalytic activity (2.1- to 24.9-fold) relative to β-ketiminates. The polymerization results demonstrated that swapping oxygen atoms for sulfur atoms in β-ketiminate-associated Al complexes improved the catalytic activity of Al complexes for CL ROP.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"42 23\",\"pages\":\"3405–3417\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2023-11-15\",\"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.3c00383\",\"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.3c00383","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Effects of Aluminum Complexes Bearing β-Thioketiminate and β-Ketiminates on ε-Caprolactone Ring-Opening Polymerization Reactivity
In this study, a series of Al complexes bearing β-ketiminates and β-thioketiminates were synthesized and used as catalysts in ε-caprolactone (CL) polymerization. SPr–Al had the highest catalytic activity among all Al complexes bearing β-thioketiminates and was more active than OPr–Al (2.8 times as high for CL polymerization) ([CL]/[SPr–Al]/[BnOH] = 100:1:2, [SPr–Al] = 0.02 M, conversion = 96% after 20 min at 25 °C). All Al complexes bearing β-thioketiminates exhibited higher catalytic activity (2.1- to 24.9-fold) relative to β-ketiminates. The polymerization results demonstrated that swapping oxygen atoms for sulfur atoms in β-ketiminate-associated Al complexes improved the catalytic activity of Al complexes for CL ROP.
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.
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