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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
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
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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 [Ce4(μ3-O)2(SiW9O34)2(CH3COO)2]10– (1), [U4(μ3-O)2(SiW9O34)2(CH3COO)2]10– (2), [Th3(μ3-O)(μ2-OH)3(SiW9O34)2]13– (3), and [Hf3(μ2-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] 4)2 Ce(上NO 3)6),5D(的HfCl 4),或5F(UCL 4和Th(NO 3)4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 34)2(CH 3 COO)2 ] 10-(1) ,[U 4(μ 3 -O)2(硅钨酸9 ö 34)2(CH 3 COO)2 ] 10-(2),[钍3(μ 3 -O)(μ 2 -OH)3(硅钨酸9 ö 34)2 ] 13-(3),和[HF 3(μ 2 -OH)3(硅钨酸9 ö 34)2 ] 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1和2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
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] 4)2 Ce(上NO 3)6),5D(的HfCl 4),或5F(UCL 4和Th(NO 3)4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 34)2(CH 3 COO)2 ] 10-(1) ,[U 4(μ 3 -O)2(硅钨酸9 ö 34)2(CH 3 COO)2 ] 10-(2),[钍3(μ 3 -O)(μ 2 -OH)3(硅钨酸9 ö 34)2 ] 13-(3),和[HF 3(μ 2 -OH)3(硅钨酸9 ö 34)2 ] 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1和2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。