原位光反应法合成过氧桥连草酸铀酰配合物

在室温和实验室灯光照射条件下, 通过原位光化学反应, 分别以乙二胺和二亚乙基三胺为模板, 合成3种过氧桥连的草酸铀酰配合物NH₃(CH₂)₂NH₃]₃(UO₂)₂O₂(C₂O₄)₄]·4H₂O (1), NH₃(CH₂)₂NH₂(CH₂)₂NH₃]₂(UO₂)₂O₂(C₂O₄)₄]·2H₂O (2)和NH₃(CH₂)₂NH₂(CH₂)₂NH₃]₂(UO₂)₂O₂(C₂O₄)₄] (3)。借助单晶X射线衍射、拉曼光谱(Raman)、粉末X射线衍射(PXRD)和热重分析(TGA), 对配合物的结构及其性质进行表征和分析。1和2中U-O₂-U二面角为180°, 而通常过氧配合物的过氧二面角小于180°。2和3中过氧键的键长比正常的过氧键长短, 其中2更接近超氧键的键长, 但价态和拉曼图谱都表明其为过氧键。

Synthesis of Oxalate Peroxo-uranyl Complex in situ by Photoreaction

NH₃(CH₂)₂NH₃]₃(UO₂)₂O₂(C₂O₄)₄]·4H₂O (1), NH₃(CH₂)₂NH₂(CH₂)₂NH₃]₂(UO₂)₂O₂(C₂O₄)₄]·2H₂O (2) and NH₃(CH₂)₂NH₂(CH₂)₂NH₃]₂(UO₂)₂O₂(C₂O₄)₄] (3) were synthesized in situ under room temperature and laboratory lamp condition, using 1,2-diaminoethane and 2,2'-diaminodiethylamine separately as templates. Structures and properties were characterized by single-crystal X-ray diffraction, Raman spectra, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The dihedral angle of U-O₂-U in 1 and 2 is 180°, which deviates from the natural angle of peroxide. The peroxide bond length of 2 and 3 is shorter than that of the reported peroxide, and the bond lenth of 2 is close to superoxide bond length. However, both valence and Raman spectra indicated that 2 and 3 are peroxide bonds.