Acta Scientiarum Naturalium Universitatis Pekinensis ›› 2020, Vol. 56 ›› Issue (3): 399-405.DOI: 10.13209/j.0479-8023.2020.016

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Synthesis of Oxalate Peroxo-uranyl Complex in situ by Photoreaction

WEI Wenqi, LIU Chunli†   

  1. Beijing National Laboratory for Molecular Sciences, Fundamental Science Laboratory on Radiochemistry and Radiation Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
  • Received:2019-03-15 Revised:2019-06-06 Online:2020-05-20 Published:2020-05-20
  • Contact: LIU Chunli, E-mail: liucl(at)pku.edu.cn

原位光反应法合成过氧桥连草酸铀酰配合物

魏文琦, 刘春立†   

  1. 北京分子科学国家研究中心, 放射化学与辐射化学重点学科实验室, 北京大学化学与分子工程学院, 北京 100871
  • 通讯作者: 刘春立, E-mail: liucl(at)pku.edu.cn
  • 基金资助:
    国家自然科学基金(11475008, U1530112, U1730245)资助

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Abstract:

[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.

Key words: uranyl complex, peroxide, in situ, photoreaction, oxalic acid

摘要：

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。

关键词: 铀酰配合物, 过氧, 原位, 光反应, 草酸

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