A. O. Tolpygin, A. V. Cherkasov, G. K. Fukin, A. A. Trifonov
{"title":"双（氨基酸）氨基配合物{2-[Ph2Р(O)]C6H4NC(But)N(2,6- me2c6h3)}2LaN(SiMe3)2: racc -丙交酯和ε-己内酯开环聚合的合成、结构和催化活性","authors":"A. O. Tolpygin, A. V. Cherkasov, G. K. Fukin, A. A. Trifonov","doi":"10.1134/S107032842560041X","DOIUrl":null,"url":null,"abstract":"<p>The La(III) bis(amidinate) amido complex {2-[Ph<sub>2</sub>Р(O)]C<sub>6</sub>H<sub>4</sub>NC(Bu<sup><i>t</i></sup>)N(2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)}<sub>2</sub>LaN(SiMe<sub>3</sub>)<sub>2</sub> (<b>I</b>) was synthesized by the reaction of 2-[Ph<sub>2</sub>Р(O)]C<sub>6</sub>H<sub>4</sub>NHC(Bu<sup><i>t</i></sup>)=N(2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) (HL) and La[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>3</sub> in 2 : 1 molar ratio and isolated in 74% yield. X-ray analysis revealed that in <b>I</b> both monoanionic amidinate ligands are κ<sup>3</sup>-N,N,O-coordinated to La(III) ion. Complex <b>I</b> demonstrates high catalytic activity in ring-opening polymerization of cyclic esters and enables 100% conversion of 100–300 equiv of <i>rac</i>-lactide in 30 min or 100–500 equiv of ε-caprolactone in 1 min providing highly controlled polymerization. The obtained polymeric samples feature linear dependence of molecular weight vs. the monomer loading and rather narrow polydispersity (<i>M</i><sub>w</sub>/<i>M</i><sub><i>n</i></sub> = 1.36–1.88).</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"51 5","pages":"374 - 380"},"PeriodicalIF":1.1000,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Lanthanum Bis(amidinate) Amido Complex {2-[Ph2Р(O)]C6H4NC(But)N(2,6-Me2C6H3)}2LaN(SiMe3)2: Synthesis, Structure, and Catalytic Activity in Ring-Opening Polymerization of rac-Lactide and ε-Caprolactone\",\"authors\":\"A. O. Tolpygin, A. V. Cherkasov, G. K. Fukin, A. A. Trifonov\",\"doi\":\"10.1134/S107032842560041X\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The La(III) bis(amidinate) amido complex {2-[Ph<sub>2</sub>Р(O)]C<sub>6</sub>H<sub>4</sub>NC(Bu<sup><i>t</i></sup>)N(2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>)}<sub>2</sub>LaN(SiMe<sub>3</sub>)<sub>2</sub> (<b>I</b>) was synthesized by the reaction of 2-[Ph<sub>2</sub>Р(O)]C<sub>6</sub>H<sub>4</sub>NHC(Bu<sup><i>t</i></sup>)=N(2,6-Me<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) (HL) and La[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>3</sub> in 2 : 1 molar ratio and isolated in 74% yield. X-ray analysis revealed that in <b>I</b> both monoanionic amidinate ligands are κ<sup>3</sup>-N,N,O-coordinated to La(III) ion. Complex <b>I</b> demonstrates high catalytic activity in ring-opening polymerization of cyclic esters and enables 100% conversion of 100–300 equiv of <i>rac</i>-lactide in 30 min or 100–500 equiv of ε-caprolactone in 1 min providing highly controlled polymerization. The obtained polymeric samples feature linear dependence of molecular weight vs. the monomer loading and rather narrow polydispersity (<i>M</i><sub>w</sub>/<i>M</i><sub><i>n</i></sub> = 1.36–1.88).</p>\",\"PeriodicalId\":759,\"journal\":{\"name\":\"Russian Journal of Coordination Chemistry\",\"volume\":\"51 5\",\"pages\":\"374 - 380\"},\"PeriodicalIF\":1.1000,\"publicationDate\":\"2025-07-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Russian Journal of Coordination Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S107032842560041X\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Coordination Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S107032842560041X","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Lanthanum Bis(amidinate) Amido Complex {2-[Ph2Р(O)]C6H4NC(But)N(2,6-Me2C6H3)}2LaN(SiMe3)2: Synthesis, Structure, and Catalytic Activity in Ring-Opening Polymerization of rac-Lactide and ε-Caprolactone
The La(III) bis(amidinate) amido complex {2-[Ph2Р(O)]C6H4NC(But)N(2,6-Me2C6H3)}2LaN(SiMe3)2 (I) was synthesized by the reaction of 2-[Ph2Р(O)]C6H4NHC(But)=N(2,6-Me2C6H3) (HL) and La[N(SiMe3)2]3 in 2 : 1 molar ratio and isolated in 74% yield. X-ray analysis revealed that in I both monoanionic amidinate ligands are κ3-N,N,O-coordinated to La(III) ion. Complex I demonstrates high catalytic activity in ring-opening polymerization of cyclic esters and enables 100% conversion of 100–300 equiv of rac-lactide in 30 min or 100–500 equiv of ε-caprolactone in 1 min providing highly controlled polymerization. The obtained polymeric samples feature linear dependence of molecular weight vs. the monomer loading and rather narrow polydispersity (Mw/Mn = 1.36–1.88).
期刊介绍：
Russian Journal of Coordination Chemistry is a journal that publishes reviews, original papers, and short communications on all aspects of theoretical and experimental coordination chemistry. Modern coordination chemistry is an interdisciplinary science that makes a bridge between inorganic, organic, physical, analytical, and biological chemistry.
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