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首页> 外文期刊>Chemistry: A European journal >Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand
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Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand

机译：块状2,6-二异丙基-N-（三甲基甲硅烷基）苯胺基配体的碱金属和碱金属镁酸盐化学结构的多样性

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摘要

Bulky amido ligands are precious in s-block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe3)(Dipp)](-) (Dipp= 2,6-iPr(2)-C6H3). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by N, N, N', N '', N ''-pentamethyldiethylenetriamine (PMDETA) or N, N, N', N'-tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe3)(Dipp)}(2)(mu-nBu)](infinity) (M= Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.
机译：庞大的酰胺基配体在S嵌段化学中很珍贵，因为它们可以在化合物中植入互补的强碱性和弱亲核性质。最近的工作表明，对于含有混合的正丁基/酰胺基配体对的环状碱金属菱镁酸盐，增强碱度和非凡的区域选择性对基础结构至关重要。这项工作推进了庞大的芳基甲硅烷基酰胺基配体[N（SiMe3）（Dipp）]（-）（Dipp = 2,6-iPr（2）-C6H3）的碱金属和碱金属镁酸盐化学反应。公开了母体钠和钾酰胺的无限链结构，将其添加到少数已知的晶体学表征的未溶剂化的s-嵌段金属酰胺中。用N，N，N′，N′，N′-五甲基二亚乙基三胺（PMDETA）或N，N，N′，N′-四甲基乙二胺（TMEDA）进行溶剂化，得到酰胺化锂和钠的分子。对于钾，PMDETA提供分子结构，而TMEDA提供新颖的半溶剂化无限链。还揭示了[MMg {N（SiMe3）（Dipp）}（2）（mu-nBu）]（无穷大）（M = Na或K）中该酰胺的第一镁盐实例的晶体结构通过NMR和DOSY研究揭示了供体溶剂中的均金属成分。

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