Structural characterization of mono-ruthenium substituted Keggin-type silicotungstates.
Structural characterization of mono-ruthenium substituted Keggin-type silicotungstates.
复制标题
DOI：
10.1039/b606266k
复制
发表时间：
2006-08
影响因子：
4
通讯作者：
M. Sadakane;Daisuke Tsukuma;M. Dickman;B. Bassil;U. Kortz;M. Higashijima;W. Ueda
中科院分区：
文献类型：
--
作者：
M. Sadakane;Daisuke Tsukuma;M. Dickman;B. Bassil;U. Kortz;M. Higashijima;W. Ueda
以单缺位硅钨酸盐前驱体[SiW(11)O(39)](8-)和Ru(Acac)(3)为原料，在水热条件下合成了单Ru取代的Keggin硅钨酸盐[SiW(11)O(39)Ru(III)(H(2)O)](5-)(1a)，分离得到铯盐Cs(5)[SiW(11)O(39)Ru(III)(H(2)O)](1)。通过1a与DMSO在353K的水溶液中反应，得到了DMSO配位的配合物[SiW(11)O(39)Ru(III)(DMSO)](5-)(2a)，分离得到铯-钾混合盐Cs(4.9)K(0.1)[SiW(11)O(39)Ru(III)(DMSO)](2)。化合物1和2均经单晶X-射线结构分析、粉末X-射线结构分析、紫外-可见光谱、循环伏安、红外光谱和元素分析表征。1属四方空间群P4(2)/nCm，晶胞参数为a=20.9299(4)，c=10.3603(4)Angstrom，Z=4。由于无序，Keggin基团中的Ru原子与钨原子不能区分。2(单斜晶系，P2(1)/c，a=13.5850(4)，b=20.2764(7)，c=18.1326(4)Angstrom，β=90.8730(10)度，Z=4)的结构分析成功地揭示了DMSO通过Ru-S键与Ru原子配位。聚阴离子2a代表第一个单取代的Keggin离子，其中Ru中心没有结晶学上的无序。UV-Vis光谱结合控制电位电解证实了1和2中的Ruthenium以+3的价态存在。1和2的红外光谱非常相似。所有这些数据表明，单缺位硅钨酸盐K(8)[SiW(11)O(39)]与Ru(Acac)(3)在水热条件下反应合成的1确实是单Ru取代的Keggin类型的硅钨酸盐。
We have synthesized the mono-ruthenium substituted Keggin-type silicotungstate [SiW(11)O(39)Ru(III)(H(2)O)](5-) (1a) by reaction of the mono-lacunary silicotungstate precursor [SiW(11)O(39)](8-) with Ru(acac)(3) under hydrothermal conditions and isolated as the caesium salt Cs(5)[SiW(11)O(39)Ru(III)(H(2)O)] (1). The DMSO-coordinated complex [SiW(11)O(39)Ru(III)(DMSO)](5-) (2a) was prepared by reaction of 1a with DMSO in aqueous solution at 353 K and isolated as the caesium-potassium mixed salt Cs(4.9)K(0.1)[SiW(11)O(39)Ru(III)(DMSO)] (2). Both compounds 1 and 2 were characterized by single-crystal X-ray structure analysis, powder X-ray structure analysis, UV-Vis spectroscopy, cyclic voltammetry, IR-spectroscopy and elemental analysis. 1 crystallized in the tetragonal space group P4(2)/ncm with a = 20.9299(4), c = 10.3603(4) Angstrom, Z = 4. The ruthenium atom in the Keggin unit could not be distinguished from the tungsten due to disorder. The structural analysis of 2 (monoclinic, P2(1)/c, a = 13.5850(4), b = 20.2764(7), c = 18.1326(4) Angstrom, beta = 90.8730(10) degrees , Z = 4) successfully revealed that the incorporated ruthenium atom is coordinated by DMSO through a Ru-S bond. Polyanion 2a represents the first mono-substituted Keggin ion in which the ruthenium center is not crystallographically disordered. UV-Vis spectroscopy combined with controlled potential electrolysis confirmed that the incorporated rutheniums in 1 and 2 have a valence state of +3. The IR spectra of both 1 and 2 were very similar. All these data indicate that 1 synthesized by reaction of the mono-lacunary silicotungstate K(8)[SiW(11)O(39)] with Ru(acac)(3) under hydrothermal conditions is truly the mono-ruthenium substituted Keggin-type silicotungstate.