从Thor到to：Act系元素氯化物结构化学的趋势,Inorganic Chemistry

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从Thor到to：Act系元素氯化物结构化学的趋势
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2019-07-12 00:00:00 , DOI: 10.1021/acs.inorgchem.9b01279
Jennifer N. Wacker ₁ , Sae Young Han ₁ , Aphra V. Murray ₁ , Nicole A. Vanagas ₁ , Jeffery A. Bertke ₁ , Joseph M. Sperling ₂ , Robert G. Surbella ₃ , Karah E. Knope ₁

Affiliation

从含有th，铀或p和一系列质子化氮杂环的酸性水溶液中合成了十八种四价act系化合物（An = Th，U，Pu）。使用拉曼光谱，红外光谱和光学吸收光谱对化合物进行表征。使用单晶X射线衍射确定结构，发现其结构由[An（H ₂ O）_x Cl _y ] ^{4- y}（x = 4-7和y = 2-4）或AnCl ₆^2–分子组成单位。观察到早期act系元素的化学结构发生了断裂，其中Th仅采用Th-aquo-氯物种，Pu仅形成PuCl ₆^2–; U结晶为U–aquo–chloro和UCl ₆^2–。固态结构单元和溶液种类之间的关系使用紫外可见近红外吸收光谱法进行了研究。溶液和固态光谱的比较表明，尽管固态存在，特别是对于U和Pu，但AnCl ₆^2-在反应溶液中并不存在。尽管已鉴定出溶液中的U-aqua-氯物种，但有关固态复合物的报道很少。如本工作中所报告的，这些独特的act系元素氯化物的分离可能表明非键合相互作用在^IV结构单元的稳定和沉淀中的重要性。

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From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry

A series of eighteen tetravalent actinide (An = Th, U, Pu) compounds were synthesized from acidic aqueous solutions containing thorium, uranium, or plutonium and a series of protonated nitrogen heterocycles. The compounds were characterized using Raman, IR, and optical absorption spectroscopies. The structures were determined using single-crystal X-ray diffraction and found to consist of [An(H₂O)_xCl_y]^4–y (x = 4–7 and y = 2–4) or AnCl₆^2– molecular units. Breaks in the structural chemistry of the early actinides were observed, with Th adopting exclusively Th–aquo–chloro species and Pu forming only PuCl₆^2–; U crystallized as both U–aquo–chloro and UCl₆^2–. The relationship between the solid-state structural units and the solution species was interrogated using UV–vis–near-IR absorption spectroscopy. A comparison of the solution and solid-state spectra suggested that, although prevalent in the solid state, particularly for U and Pu, AnCl₆^2– does not exist to an appreciable extent in the reaction solution. Despite the identification of U–aquo–chloro species in solution, there are limited reports of these complexes in the solid state. Isolation of these unique actinide(IV) chlorides as reported in this work may point to the importance of nonbonding interactions in the stabilization and precipitation of An^IV structural units.

更新日期：2019-07-12

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