Ion Dynamics in Confined Spaces: Sodium Ion Mobility in Icosahedral Container Molecules
Ion Dynamics in Confined Spaces: Sodium Ion Mobility in Icosahedral Container Molecules
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DOI：
10.1002/anie.201003441
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Gruetzmacher, Hansjoerg
中科院分区：
文献类型：
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作者：
Podewitz, Maren;van Beek, Jacco D.;Gruetzmacher, Hansjoerg
在晶体中的分子阴离子配体框架内的阳离子波动很少被观察到。Veith等人已经研究了含有阴离子（N-Si-O-Si-N）2 =（X2）或（O-Si-N-Si-O）=（Z）骨架的结晶酰胺锂中的局部Li+离子波动。[1]在[Li 2（Z）2]和[Li 4（X）2]晶体中，金属离子的运动是以协同的方式进行的，即阳离子同时从充满的位置跳跃到空的位置，形成静电耦合的（Li 2）2+和（Li 4）4+团簇，这种运动与原子和原子团的相变、旋转和振荡有关。在“洋葱”型球形团簇[Li_（24）OI_2（AsR）_（10）]（R= Me_2（iPrMe_2C）Si）中也发现了Li ~+离子的部分动力学无序。[2]迄今为止，在结晶的“分子盒”中的离子波动仅被观察到Li+ ions.We在此报告的两个化合物，这是由一个小的中心PH 2 <$阴离子包围的球形外壳由十二叔丁氧基阴离子组成。在这个有限的聚阴离子空间中，即在PH 2阴离子和外壳之间，嵌入了12或13个高度移动的钠阳离子。一个钠离子可以可逆地加入或除去，以使这些聚集体相互转化。Brandsma等人报道了磷化二氢钠（NaPH 2）的合成，其使用金属钠还原元素磷并随后加入叔丁醇。这种形式的NaPH 2是制备有机磷化合物的通用试剂;[3]然而，这种“Brandsma试剂”的性质尚不清楚。
Cation fluctuations within a molecular anionic ligand framework in crystals have rarely been observed. Veith et al. have studied local Li+ ion fluctuations in crystalline lithium siloxyamides that contain either an anionic (N-Si-O-Si-N) 2¿=(X2¿) or (O-Si-N-Si-O)¿=(Z¿) skeleton.[1] In the crystalline [Li2 (Z) 2] and [Li4 (X) 2] species, the metal movements proceed in a concerted fashion, that is, the cations jump simultaneously from filled to empty positions as electrostatically coupled (Li2) 2+ and (Li4) 4+ clusters, and the movements are linked to phase transitions, rotations, and oscillations of atoms and atom groups. A partial dynamic disorder of Li+ ions has also been reported in the “onion”-type spherical cluster [Li24OI2 (AsR) 10](R= Me2 (iPrMe2C) Si).[2] To date, ion fluctuations in crystallized “molecular boxes” have only been observed for Li+ ions.We report herein on two compounds that are composed of a small central PH2¿ anion surrounded by a spherical outer shell consisting of twelve tert-butoxy anions. In this confined polyanionic space, that is, between the PH2¿ anion and the outer shell, 12 or 13 highly mobile sodium cations are embedded. One sodium ion can be reversibly added or removed to interconvert these aggregates. Brandsma et al. reported the synthesis of sodium dihydrogenphosphide, NaPH2, which uses the reduction of elemental phosphorus with sodium metal and subsequent addition of tert-butyl alcohol. This form of NaPH2 is a versatile reagent for the preparation of organophosphorus compounds;[3] however, the nature of this “Brandsma reagent” was not known.