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Probing the Influence of Acidity and Temperature to Th(IV) on Hydrolysis, Nucleation, and Structural Topology
Inorganic Chemistry ( IF 4.6 ) Pub Date : 2017-11-08 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02335
Jian Lin 1 , Meiying Qie 1 , Linjuan Zhang 1 , Xiaomei Wang 1 , Yuejian Lin 2 , Wei Liu 3 , Hongliang Bao 1 , Jianqiang Wang 1
Affiliation  

Systematic control of the molar ratio between thorium hydroxides and selenic acid and their reaction temperature under hydrothermal conditions results in four novel thorium-based selenate complexes, namely, [Th8O4(OH)8(SeO4)6(H2O)16]·(SeO4)2·13H2O (Th-1), [Th8O4(OH)8(SeO4)8(H2O)13]·7H2O (Th-2), Th(OH)2(SeO4)H2O (Th-3), and Th3(SeO4)6(H2O)6·2.5H2O (Th-4), as well as the thorium mixed selenite selenate compound Th(SeO3)(SeO4) (Th-5). Smaller [H2SeO4]/[Th(IV)] ratio or lower temperature give rise to the formation of octameric [Th83-O)42-OH)8]16+ cores in Th-1/Th-2 and infinite [Th(μ2-OH)2H2O]2+ chains in Th-3, respectively. Increasing the [H2SeO4]/[Th(IV)] ratio or elevating the temperature generates a microporous (11.3 Å voids) open-framework Th-4, a monomeric thorium species without oxo/hydroxyl ligands, and a three-dimensional thorium structure Th-5. Formation of these compounds suggests that variables including acidity and temperature play a critical role in the hydrolysis and oligomerization of ThIV ions. Increasing acidity limits the deprotonation of water molecules and formation of nucleophilic hydroxo/oxo-aquo Th species, and high temperature appears to suppress the olation/oxolation hydrolysis reactions, which in both ways limit the formation of the thorium oligomers.

中文翻译:

探索酸度和温度对Th(IV)对水解,成核和结构拓扑的影响

在水热条件下系统地控制氢氧化or与硒酸之间的摩尔比及其反应温度可产生四种新型的based基硒酸盐配合物,即[Th 8 O 4(OH)8(SeO 46(H 2 O)16 ]·(SEO 42 ·13H 2 O(- 1),[钍8 ø 4(OH)8(SEO 48(H 2 O)13 ]·7H 2 O(-2),Th(OH)2(SeO 4)H 2 O(Th - 3)和Th 3(SeO 46(H 2 O)6 ·2.5H 2 O(Th - 4)以及mixed混合亚硒酸盐硒酸盐化合物Th(SeO 3)(SeO 4)(Th - 5)。较小的[H 2的SeO 4 ] / [钍(IV)]的比值或更低的温度下产生八聚体的形成[钍8(μ 3 -O)4(μ2 -OH)8 ] 16+芯中的Th-1 /钍-2 [钍(μ和无限2 -OH)2 ħ 2 O] 2+链中的Th-3分别。增加[H 2 SeO 4 ] / [Th(IV)]的比例或升高温度会生成微孔(11.3Å空隙)的开放骨架Th-4,无氧/羟基配体的th单体和三维-5结构Th-5。这些化合物的形成表明,酸度和温度等变量在Th IV的水解和低聚中起关键作用。离子。酸度的增加限制了水分子的去质子化和亲核羟基/羰基水族Th物种的形成,并且高温似乎抑制了羟基化/羟基化水解反应,这两种方式都限制了or低聚物的形成。
更新日期:2017-11-08
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