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Stabilization of Tetravalent 4f (Ce), 5d (Hf), or 5f (Th, U) Clusters by the [α-SiW9O34]10– Polyoxometalate
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2015-08-24 00:00:00 , DOI: 10.1021/acs.inorgchem.5b00786
Sylvain Duval 1 , Sébastien Béghin 1 , Clément Falaise 1 , Xavier Trivelli 2 , Pierre Rabu 3, 4 , Thierry Loiseau 1
Affiliation  

The reaction of Na10[α-SiW9O34] with tetravalent metallic cations such as 4f ((NH4)2Ce(NO3)6), 5d (HfCl4), or 5f (UCl4 and Th(NO3)4) in a pH 4.7 sodium acetate buffer solution leads to the formation of four sandwich-type polyoxometalates [Ce43-O)2(SiW9O34)2(CH3COO)2]10– (1), [U43-O)2(SiW9O34)2(CH3COO)2]10– (2), [Th33-O)(μ2-OH)3(SiW9O34)2]13– (3), and [Hf32-OH)3(SiW9O34)2]11– (4). All four compounds consist of a polynuclear cluster fragment stabilized by two [α-SiW9O34]10– polyanions. Compounds 1 and 2 are isostructural with a tetranuclear core (Ce4, U4), while compound 3 presents a trinuclear Th3 core bearing a μ3-O-centered bridge. It is an unprecedented configuration in the case of the thorium(IV) cluster. Compound 4 also possesses a trinuclear Hf3 core but with the absence of the μ3-O bridge. The molecules have been characterized by single-crystal X-ray diffraction, 183W and 29Si nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) analysis.

中文翻译:

四价4F(铈)的稳定化,图5d(HF),或5F(Th时,U)由[α-硅钨酸集群9 ö 34 ] 10-多金属氧酸盐

钠的反应10 [α-硅钨酸9 ö 34与四价金属阳离子如4F((NH] 42 Ce(上NO 36),5D(的HfCl 4),或5F(UCL 4和Th(NO 34在pH 4.7的醋酸钠缓冲溶液通向四个夹层型多金属氧酸盐的形成)[CE 4(μ 3 -O)2(硅钨酸9 ö 342(CH 3 COO)2 ] 10-1) ,[U 4(μ 3 -O)2(硅钨酸9 ö 342(CH 3 COO)2 ] 10-2),[钍3(μ 3 -O)(μ 2 -OH)3(硅钨酸9 ö 342 ] 13-3),和[HF 3(μ 2 -OH)3(硅钨酸9 ö 342 ] 11-4)。所有四种化合物包括由两个[α-硅钨酸稳定的多核簇片段的9 ö 34 ] 10-聚阴离子。化合物12是同构与四核芯(铈4,U 4),而化合物3所呈现出三核的Th 3芯轴承μ 3 -O-居中桥。对于or(IV)簇而言,这是前所未有的配置。化合物4还具有三核的Hf 3芯,但与不存在μ的3 -O桥。这些分子已通过单晶X射线衍射表征,183 W和29 Si核磁共振(NMR)光谱,红外(IR)光谱,热重分析(TGA)和扫描电子显微镜/能量色散X射线(SEM / EDX)分析。
更新日期:2015-08-24
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