The Discrete AlF52- Fluoroaluminate Anion in the Structure of [Tetraethylammonium]2[AlF5](H2O)2
The Discrete AlF52- Fluoroaluminate Anion in the Structure of [Tetraethylammonium]2[AlF5](H2O)2
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DOI：
10.1002/ejic.201501036
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发表时间：
2015-11-01
影响因子：
2.3
通讯作者：
Hagiwara, Rika
中科院分区：
文献类型：
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作者：
Veryasov, Gleb;Matsumoto, Kazuhiko;Hagiwara, Rika
通过对[Et4N](2)[AlF5](H2O)(2)(Et4N+=四乙基铵)(Et4N+=四乙基铵)单晶的X-射线单晶分析，首次确定了分立型氟铝酸根阴离子(AlF52-)的晶体结构。通过两个当量的[Et4N][AlF4]与[Me4N]F(Me4N+=四甲铵)反应，故意制备了含有Al2F93-离子的化合物，导致了[Et4N][Me4N][AlF5]与未反应的[Et4N][AlF4]的生成。在[Et4N](2)[AlF5](H2O)(2)作为含有三角双锥AlF52-阴离子的沉淀物的存在下，这些物种之间的阳离子交换。本研究的数据允许补充元素周期表第三周期的配体紧密堆积(LCP)模型。在量子化学计算的基础上，分析了[Et4N](2)[AlF5](H2O)(2)的拉曼光谱。
The first crystallographically defined example of the discrete fluoroaluminate anion (AlF52-) was elucidated by analysis of single crystals of [Et4N](2)[AlF5](H2O)(2) (Et4N+ = tetraethylammonium) by X-ray crystallography. Intentional preparation of a compound containing the Al2F93- anion by the reaction of two equivalents of [Et4N][AlF4] with [Me4N]F (Me4N+ = tetramethylammonium) resulted in the formation of [Et4N][Me4N][AlF5] with unreacted [Et4N][AlF4]. Cation exchange between these species in the presence of water furnished [Et4N](2)[AlF5](H2O)(2) as a precipitate containing the trigonal bipyramidal AlF52- anion. The data from the present study allows supplementing the ligand close packing (LCP) model for the third period of the periodic table. The Raman spectrum of [Et4N](2)[AlF5](H2O)(2) was analyzed on the basis of quantum chemical calculations.