U(methylenediphosphonato)(H2O) | 1029348-15-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: U(methylenediphosphonato)(H2O)
• CAS: 1029348-15-9
• 化学式: CH₂O₆P₂*H₂O*U
• 分子量: 428.015
• InChiKey: SJWVHRVBCIZIRU-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  -4.05
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  157.88
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  亚甲基二磷酸 、 水 、 uranium(VI) trioxide 以 水 为溶剂， 生成 U(methylenediphosphonato)(H2O) 、 uranyl methylenediphosphonate(2-) monohydrate
  参考文献：
  名称：

  Further Examples of the Failure of Surrogates to Properly Model the Structural and Hydrothermal Chemistry of Transuranium Elements: Insights Provided by Uranium and Neptunium Diphosphonates

  摘要：

  In situ hydrothermal reduction of Np(VI) to Np(IV) in the presence of methylenediphosphonic acid (C1P2) results in the crystallization of Np[CH2(PO3)(2)](H2O)(2) (NpC1P2-1). Similar reactions have been explored with U(VI) resulting in the isolation of the U(IV) diphosphonate U[CH2(PO3)(2)](H2O) (UC1P2-1), and the two U(VI) diphosphonates (UO2)(2)[CH2(PO3)(2)](H2O)(3) center dot H2O (UC1P2-2) and UO2[CH2(PO3H)(2)](H2O) (UC1P2-3). Single crystal diffraction studies of NpC1P2-1 reveal that it consists of eight-coordinate Np(IV) bound by diphosphonate anions and two coordinating. water molecules to create a polar three-dimensional framework structure wherein the water molecules reside in channels. The structure of UC1P2-1 is similar to that of NpC1P2-1 in that it also adopts a three-dimensional structure. However, the U(IV) centers are seven-coordinate with only a single bound water molecule. UC1P2-2 and UC1P2-3 both contain U(VI), Nevertheless, their structures are quite distinct with UC1P2-2 being composed of corrugated layers containing UO6 and UO7 units bridged by C1P2; whereas, UC1P2-3 is found as a polar three-dimensional network structure containing only pentagonal bipyramidal U(VI), Fluorescence measurements on UC1P2-2 and UC1P2-3 exhibit emission from the uranyl moieties with classical vibronic fine-structure.

  DOI：

  10.1021/ic800255h

文献信息

• Systematic Investigation of the <i>in Situ</i> Reduction Process from U(VI) to U(IV) in a Phosphonate System under Mild Solvothermal Conditions
  作者：Lanhua Chen、Juan Diwu、Daxiang Gui、Yaxing Wang、Zhehui Weng、Zhifang Chai、Thomas E. Albrecht-Schmitt、Shuao Wang

  DOI：10.1021/acs.inorgchem.7b00480

  日期：2017.6.19

  by the variation of reaction conditions. The UV–vis–NIR absorption spectra of the tetravalent uranium compounds show that the absorption features are closely related to the local coordination environments of the uranium centers as well as the bonding modes of the phosphonate ligand. The fluorescence spectra of mixed-valent uranium compounds show unique emission features of U(VI) luminescence that are

  氧化态极大地影响了铀在核燃料循环和环境中的化学行为。另一方面，膦酸酯配体在不同的氧化态下表现出对铀的强络合作用，并广泛用于核燃料的后处理中。因此，在这项工作中，在温和的溶剂热条件下研究了在膦酸酯配体存在下U（VI）的还原行为。通过调整反应时间，温度和抗衡离子种类，可以得到一系列的二膦铀酸盐，包括两个U（VI），七个U（IV），两个混合价U（IV / VI）和一个不同的U（IV / V / VI）获得化合物。所有这些化合物的特征在于单晶X射线衍射，UV-vis-NIR吸收和荧光光谱。原位还原途径受反应条件变化的影响。四价铀化合物的UV-NIR吸收光谱表明，吸收特征与铀中心的局部配位环境以及膦酸酯配体的键合模式密切相关。混合价铀化合物的荧光光谱显示了U（VI）发光的独特发射特征，该特征被可见光和NIR区域中U（IV）中心的多个电子跃迁部分淬灭。