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首页> 外文期刊>Chemistry: A European journal >'Alkaline-Earth Metals in a Box': Structures of Solvent-Separated Ion Pairs
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'Alkaline-Earth Metals in a Box': Structures of Solvent-Separated Ion Pairs

机译：“盒中的碱土金属”：溶剂分离的离子对的结构

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During our research on homoleptic organocalcium compounds, we found that fluorenylcalcium complexes show unusual solution behavior and precipitate from nonpolar solvents after addition of THF. Their solid-state structures reveal the unexpected rupture of both metal-carbanion bonds by the polar solvent THF. The crystal structures of five new Mg and Ca solvent-separated ion pairs are described. The compound [Ca~(2+)(thf)_6]-[Me_3Si(fluorenyl~-)_2] is the first organometallic complex of a Group 2 element that crystallizes as a completely solvent-separated ion pair. The driving forces for its formation are: 1) the strong Ca-THF bond; 2) the stability of the free [Me_2Si(fluorenyl)]~- ion; 3) encapsulation of [Ca~(2+)(thf)_6] in a "box", the walls of which consist of anionic fluorenyl ligands and benzene molecules; and 4) the presence of numerous (THF)C-H…#pi# interactions.t eh magnesium analogue [Mg~(2+)(thf)_6][Me_3Si(fluorenyl~-)]_2 is isostructural. Bis(7,9-diphenylcyclopenta[a]acenaphthadienyl)calcium also crystallizes as a completely solvent-separated ion pair and can likewise be described as a [Ca~(2+)(thf)_6] species ina box of delocalized anions and benzen molecules. In addition, the structures of two Ph_4B- complexes of Mg and Ca are described. [Mg~(2+)(thf)_6][Ph_4B~-]_2 crystallizes as a completely solvent-separated ion pair and also shows a solvated metal cation bonded via C-H…#pi# interactions in a cavity formed by Ph_4B~- ions. [(thf)_4CaBr~+][Ph_4B~-] has a structure in which one of the anionic ligands is still bonded to the Ca atom. Bridging bromide ligands result in the formation of the dimer [(thf)_4CaBr~+]_2.
机译：在我们对均相有机钙化合物的研究中，我们发现芴基钙络合物显示出异常的溶液行为，并在添加THF后从非极性溶剂中沉淀出来。它们的固态结构表明极性溶剂THF会意外破坏两个金属-碳负离子键。描述了五个新的Mg和Ca溶剂分离的离子对的晶体结构。化合物[Ca〜（2 +）（thf）_6]-[Me_3Si（芴基-）_ 2]是第2组元素的第一个有机金属配合物，其结晶为完全溶剂分离的离子对。其形成的驱动力是：1）强大的Ca-THF键; 2）游离[Me_2Si（芴基）]〜-离子的稳定性; 3）将[Ca〜（2 +）（thf）_6]封装在一个“盒子”中，其壁由阴离子芴基配体和苯分子组成; 4）镁类似物[Mg〜（2 +）（thf）_6] [Me_3Si（芴基〜-）] _ 2是同构的。双（7,9-二苯基环戊[a] ac萘二烯基）钙也结晶为完全溶剂分离的离子对，同样可以在离域阴离子和苯的盒子中描述为[Ca〜（2 +）（thf）_6]种类。分子。另外，描述了Mg和Ca的两个Ph_4B-配合物的结构。 [Mg〜（2 +）（thf）_6] [Ph_4B〜-] _ 2结晶为溶剂完全分离的离子对，并且在由Ph_4B〜-形成的腔中还显示出通过CH…＃pi＃相互作用键合的溶剂化金属阳离子。离子。 [（thf）_4CaBr〜+] [Ph_4B〜-]具有其中一种阴离子配体仍与Ca原子键合的结构。桥接溴化物配体导致形成二聚体[（thf）_4CaBr〜+] _ 2。

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