Qiongli Liu, Dianyong Yang, Xiuge Zhao, Zhiwei Xu, Ji Ding, Danqi Wu, Ning An, Huiying Liao, Zhenshan Hou
{"title":"用聚合物支撑的 Ni-Salen 催化剂氧化裂解木质素模型化合物中的β-O-4 键","authors":"Qiongli Liu, Dianyong Yang, Xiuge Zhao, Zhiwei Xu, Ji Ding, Danqi Wu, Ning An, Huiying Liao, Zhenshan Hou","doi":"10.1039/d4su00331d","DOIUrl":null,"url":null,"abstract":"The transition metal-catalyzed lignin oxidative cleavage reactions have attracted considerable attention. In this work, the polymerized ionic liquid-tagged Salen ligands have been initially synthesized, followed by anion exchange, and then coordination with Ni(Ⅱ) via the -N2O2- tetradentate structure. Finally, the as-obtained Ni Salen complexes were polymerized to give a Ni-Salen polymer catalyst (poly Ni-[Salen-Vim][OAc]2). The resulting catalyst showed 99% conversion and 88% selectivity to the oxidative cleavage products for the oxidative cleavage of the lignin model compound (2-phenoxy-1-phenylethanone) without any base additive at 110°C. The polymeric ionic liquid-tagged Salen(Ni) catalysts can be separated easily by centrifugation after the reaction, and recycled for five runs with a slight loss of activity. Additionally, the studies on birch lignin depolymerization indicated that the polymer-supported Ni Salen catalyst was able to cleave the β-O-4 linkages to produce the dimeric products. The further investigation suggests that the oxidative cleavage reaction was proceeded via a radical pathway.","PeriodicalId":74745,"journal":{"name":"RSC sustainability","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Oxidative Cleavage of β-O-4 bonds in Lignin Model Compounds with Polymer-Supported Ni-Salen Catalysts\",\"authors\":\"Qiongli Liu, Dianyong Yang, Xiuge Zhao, Zhiwei Xu, Ji Ding, Danqi Wu, Ning An, Huiying Liao, Zhenshan Hou\",\"doi\":\"10.1039/d4su00331d\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The transition metal-catalyzed lignin oxidative cleavage reactions have attracted considerable attention. In this work, the polymerized ionic liquid-tagged Salen ligands have been initially synthesized, followed by anion exchange, and then coordination with Ni(Ⅱ) via the -N2O2- tetradentate structure. Finally, the as-obtained Ni Salen complexes were polymerized to give a Ni-Salen polymer catalyst (poly Ni-[Salen-Vim][OAc]2). The resulting catalyst showed 99% conversion and 88% selectivity to the oxidative cleavage products for the oxidative cleavage of the lignin model compound (2-phenoxy-1-phenylethanone) without any base additive at 110°C. The polymeric ionic liquid-tagged Salen(Ni) catalysts can be separated easily by centrifugation after the reaction, and recycled for five runs with a slight loss of activity. Additionally, the studies on birch lignin depolymerization indicated that the polymer-supported Ni Salen catalyst was able to cleave the β-O-4 linkages to produce the dimeric products. The further investigation suggests that the oxidative cleavage reaction was proceeded via a radical pathway.\",\"PeriodicalId\":74745,\"journal\":{\"name\":\"RSC sustainability\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-09-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"RSC sustainability\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1039/d4su00331d\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"RSC sustainability","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/d4su00331d","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Oxidative Cleavage of β-O-4 bonds in Lignin Model Compounds with Polymer-Supported Ni-Salen Catalysts
The transition metal-catalyzed lignin oxidative cleavage reactions have attracted considerable attention. In this work, the polymerized ionic liquid-tagged Salen ligands have been initially synthesized, followed by anion exchange, and then coordination with Ni(Ⅱ) via the -N2O2- tetradentate structure. Finally, the as-obtained Ni Salen complexes were polymerized to give a Ni-Salen polymer catalyst (poly Ni-[Salen-Vim][OAc]2). The resulting catalyst showed 99% conversion and 88% selectivity to the oxidative cleavage products for the oxidative cleavage of the lignin model compound (2-phenoxy-1-phenylethanone) without any base additive at 110°C. The polymeric ionic liquid-tagged Salen(Ni) catalysts can be separated easily by centrifugation after the reaction, and recycled for five runs with a slight loss of activity. Additionally, the studies on birch lignin depolymerization indicated that the polymer-supported Ni Salen catalyst was able to cleave the β-O-4 linkages to produce the dimeric products. The further investigation suggests that the oxidative cleavage reaction was proceeded via a radical pathway.