Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.
Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.
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DOI：
10.1002/chem.201602683
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发表时间：
2016-10-10
影响因子：
4.3
通讯作者：
Mulvey, Robert E.
中科院分区：
文献类型：
--
作者：
Fuentes, M. Angeles;Zabala, Andoni;Kennedy, Alan R.;Mulvey, Robert E.
庞大的酰胺配体在 s 嵌段化学中非常珍贵，因为它们可以在化合物中植入互补的强碱性和弱亲核特性。最近的工作表明，对于含有混合正丁基/酰胺基配体组的环状碱金属镁酸盐来说，基础结构的关键重要性在于增强碱性和非凡的区域选择性。这项工作推进了大体积芳基甲硅烷基酰胺配体 [N(SiMe3)(Dipp)]− (Dipp=2,6-iPr2-C6H3) 的碱金属和碱金属镁酸盐化学。公开了母体氨基钠和氨基钾的无限链结构，增加了少数已知的晶体学特征的非溶剂化 s-嵌段金属氨基化合物。通过 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，得到氨基锂和氨基钠的分子变体；对于钾来说，PMDETA 提供分子结构，TMEDA 提供新颖的半溶剂化无限链。还揭示了该酰胺在 [MMg{N(SiMe3)(Dipp)}2(μ-nBu)]∞（M=Na 或 K）中的第一个镁酸盐实例的晶体结构，尽管通过 NMR 和 DOSY 研究揭示了这些在供体溶剂中分解为其同金属成分。
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‐iPr2‐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(μ‐nBu)]∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.
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影响因子：
4.9
作者：
Conway, Ben;Graham, David V.;Mulvey, Robert E.
通讯作者：
Mulvey, Robert E.
DOI：
10.1039/c39940002393
发表时间：
1994-10-21
影响因子：
--
作者：
CLEGG, W;HORSBURGH, L;ROSS, MJ
通讯作者：
ROSS, MJ
影响因子：
4.9
作者：
Andrews, PC;Duggan, PJ;Nichols, PJ
通讯作者：
Nichols, PJ
影响因子：
2.3
作者：
Andrews, PC;Barnett, NDR;Wakefield, BJ
通讯作者：
Wakefield, BJ
影响因子：
4.3
作者：
Armstrong, David R.;Kennedy, Alan R.;Robertson, Stuart D.
通讯作者：
Robertson, Stuart D.