{"title":"约束还原希夫碱配体支持的同感镁和钙配合物用于丙交酯聚合：丙交酯/配体相互作用的DFT分析","authors":"Timothy Quek, Thonthun Saeteaw, Tanyawan Pongpanit, Supawadee Namuangruk and Khamphee Phomphrai","doi":"10.1039/D5CP02229K","DOIUrl":null,"url":null,"abstract":"<p >A homoleptic calcium complex supported by a constrained reduced Schiff base ligand was synthesised and found to be highly active for the ring-opening polymerisation (ROP) of 100 equiv. lactide within 2 min at room temperature. However, the magnesium analogue has significantly lower reactivity. Single-crystal X-ray diffraction revealed a 6-coordinate metal environment for both complexes. Density functional theory (DFT) calculations showed that the calcium complex can asccommodate up to 7-coordination, thereby facilitating polymerisation without detachment of the dimethylamino sidearm, unlike in the magnesium complex. The participation of the phenoxy group and secondary amine (N–H) were observed to facilitate polymerisation <em>via</em> hydrogen bonding.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 35","pages":" 18116-18120"},"PeriodicalIF":2.9000,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Homoleptic magnesium and calcium complexes supported by constrained reduced Schiff base ligand for lactide polymerisation: DFT analysis of lactide/ligand interactions\",\"authors\":\"Timothy Quek, Thonthun Saeteaw, Tanyawan Pongpanit, Supawadee Namuangruk and Khamphee Phomphrai\",\"doi\":\"10.1039/D5CP02229K\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A homoleptic calcium complex supported by a constrained reduced Schiff base ligand was synthesised and found to be highly active for the ring-opening polymerisation (ROP) of 100 equiv. lactide within 2 min at room temperature. However, the magnesium analogue has significantly lower reactivity. Single-crystal X-ray diffraction revealed a 6-coordinate metal environment for both complexes. Density functional theory (DFT) calculations showed that the calcium complex can asccommodate up to 7-coordination, thereby facilitating polymerisation without detachment of the dimethylamino sidearm, unlike in the magnesium complex. The participation of the phenoxy group and secondary amine (N–H) were observed to facilitate polymerisation <em>via</em> hydrogen bonding.</p>\",\"PeriodicalId\":99,\"journal\":{\"name\":\"Physical Chemistry Chemical Physics\",\"volume\":\" 35\",\"pages\":\" 18116-18120\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-08-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/cp/d5cp02229k\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/cp/d5cp02229k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Homoleptic magnesium and calcium complexes supported by constrained reduced Schiff base ligand for lactide polymerisation: DFT analysis of lactide/ligand interactions
A homoleptic calcium complex supported by a constrained reduced Schiff base ligand was synthesised and found to be highly active for the ring-opening polymerisation (ROP) of 100 equiv. lactide within 2 min at room temperature. However, the magnesium analogue has significantly lower reactivity. Single-crystal X-ray diffraction revealed a 6-coordinate metal environment for both complexes. Density functional theory (DFT) calculations showed that the calcium complex can asccommodate up to 7-coordination, thereby facilitating polymerisation without detachment of the dimethylamino sidearm, unlike in the magnesium complex. The participation of the phenoxy group and secondary amine (N–H) were observed to facilitate polymerisation via hydrogen bonding.
期刊介绍：
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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