{"title":"镁氢化物与二氧化碳反应生成多核镁笼化合物","authors":"Wimonsiri Huadsai, Laure Vendier, Matthias Westerhausen, Sébastien Bontemps","doi":"10.1002/zaac.202400070","DOIUrl":null,"url":null,"abstract":"The reaction of a sterically shielded Mg hydride complex, bearing a bulky β‐diketiminato (BDI) ligand, with CO2 leads to the formation of polynuclear complexes. CO2 not only inserts into the metal hydride bond yielding formate ions, but also adds onto the γ‐C of the BDI ligand. This reactivity gives rise to the formation of tri‐ and tetranuclear structures in THF, leading to a hexameric structure associated with a change in the coordination mode of the BDI ligand at 60 °C in THF within four days. The hexameric complex was isolated in high reproducible yield from the solution and characterized by X‐ray diffraction analysis. The reaction affording the hexameric complex was shown to be completed within 1 h at room temperature in toluene. Similar reactions of CO2 with a BDI calcium hydride complex proceeds less cleanly and a pure product could not be isolated.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Reaction of a Bulky β‐Diketiminato Magnesium Hydride with CO2 Yielding a Polynuclear Magnesium Cage Compound\",\"authors\":\"Wimonsiri Huadsai, Laure Vendier, Matthias Westerhausen, Sébastien Bontemps\",\"doi\":\"10.1002/zaac.202400070\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The reaction of a sterically shielded Mg hydride complex, bearing a bulky β‐diketiminato (BDI) ligand, with CO2 leads to the formation of polynuclear complexes. CO2 not only inserts into the metal hydride bond yielding formate ions, but also adds onto the γ‐C of the BDI ligand. This reactivity gives rise to the formation of tri‐ and tetranuclear structures in THF, leading to a hexameric structure associated with a change in the coordination mode of the BDI ligand at 60 °C in THF within four days. The hexameric complex was isolated in high reproducible yield from the solution and characterized by X‐ray diffraction analysis. The reaction affording the hexameric complex was shown to be completed within 1 h at room temperature in toluene. Similar reactions of CO2 with a BDI calcium hydride complex proceeds less cleanly and a pure product could not be isolated.\",\"PeriodicalId\":23934,\"journal\":{\"name\":\"Zeitschrift für anorganische und allgemeine Chemie\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-06-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Zeitschrift für anorganische und allgemeine Chemie\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1002/zaac.202400070\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Zeitschrift für anorganische und allgemeine Chemie","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/zaac.202400070","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
摘要
带有笨重的 β-二乙酰亚氨基(BDI)配体的具有立体屏蔽作用的氢化镁络合物与二氧化碳反应,会形成多核络合物。二氧化碳不仅插入金属氢化物键产生甲酸根离子,还加入到 BDI 配体的 γ-C 上。这种反应性导致在四氢呋喃中形成三核和四核结构,并在四氢呋喃中 60 °C 的四天内形成与 BDI 配体配位模式变化相关的六聚体结构。从溶液中分离出的六聚体复合物具有很高的重复产率,并通过 X 射线衍射分析对其进行了表征。生成六聚体复合物的反应在室温甲苯中 1 小时内完成。二氧化碳与 BDI 氢化钙络合物的类似反应进行得不太顺利,无法分离出纯产物。
Reaction of a Bulky β‐Diketiminato Magnesium Hydride with CO2 Yielding a Polynuclear Magnesium Cage Compound
The reaction of a sterically shielded Mg hydride complex, bearing a bulky β‐diketiminato (BDI) ligand, with CO2 leads to the formation of polynuclear complexes. CO2 not only inserts into the metal hydride bond yielding formate ions, but also adds onto the γ‐C of the BDI ligand. This reactivity gives rise to the formation of tri‐ and tetranuclear structures in THF, leading to a hexameric structure associated with a change in the coordination mode of the BDI ligand at 60 °C in THF within four days. The hexameric complex was isolated in high reproducible yield from the solution and characterized by X‐ray diffraction analysis. The reaction affording the hexameric complex was shown to be completed within 1 h at room temperature in toluene. Similar reactions of CO2 with a BDI calcium hydride complex proceeds less cleanly and a pure product could not be isolated.