plutonium(IV) hydroxide | 14014-51-8

• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 各种混合金属/非金属
• 英文名称: plutonium(IV) hydroxide
• CAS: 14014-51-8
• 化学式: H₄O₄Pu
• 分子量: 312.094
• InChiKey: GHWSWLZMLAMQTK-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  -2.23
• 重原子数：
  5.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  80.92
• 氢给体数：
  4.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  plutonium(IV) hydroxide 、 二溴化二硫 生成 plutonium(III) bromide
  参考文献：
  名称：

  Bluestein, B. A.; Garner, G. S., LA-116 (1944)

  摘要：

  DOI：
• 作为产物：
  描述：

  钚 在 ammonia 作用下， 以 aq. HNO₃ 为溶剂， 生成 plutonium(IV) hydroxide
  参考文献：
  名称：

  Disproportionation of Pu(V) in aqueous HCOOH solutions

  摘要：

  The behavior of Pu(VI), Pu(V), and Pu(IV) in the HCOOH-H2O system was studied by spectrophotometry. The Pu(VI) absorption spectrum in solutions containing less than 1 mM HClO4 changes on adding HCOOH to a concentration of 0.53 M. Along with a decrease in the intensity of the absorption maximum at 830.6 nm, corresponding to an f-f transition in the PuO22+ aqua ion, a new band arises with the maximum shifted to 834.5 nm. These transformations are due to formation of a Pu(VI) formate complex (1 : 1). The Pu(IV) absorption spectra in HCOOH solutions vary insignificantly in going from 3.0 to 9.0 M HCOOH and are similar to the spectrum of Pu(IV) in a 0.88 M HCOOH + 0.41 M NaHCOO + 0.88 M NaClO4 solution, which indicates that the composition of the Pu(IV) formate complexes is constant. Pu(V) is unstable in HCOOH solutions and disproportionates to form Pu(VI) and Pu(IV). The reaction rate is approximately proportional to [Pu(V)](2) and grows with an increase in [HCOOH]. The reaction products affect the reaction rate: Pu(IV) accelerates the process, and Pu(VI) decelerates the consumption of Pu(V) by binding Pu(V) in a cation-cation complex. The disproportionation occurs via formation of a Pu(V)-Pu(V) cation-cation complex whose thermal excitation yields an activated complex with its subsequent decomposition to Pu(VI) and Pu(IV).

  DOI：

  10.1134/s106636221001008x

文献信息

• Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes
  作者：Matthieu Audras、Laurence Berthon、Claude Berthon、Dominique Guillaumont、Thomas Dumas、Marie-Claire Illy、Nicolas Martin、Israel Zilbermann、Yulia Moiseev、Yeshayahu Ben-Eliyahu、Armand Bettelheim、Sebastiano Cammelli、Christoph Hennig、Philippe Moisy

  DOI：10.1021/acs.inorgchem.7b01666

  日期：2017.10.16

  observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H2O)]−, where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent

  通过紫外可见分光光度法，NMR光谱研究了1,4,7,10-四氮杂癸烷-1,4,7,10-四乙酸（DOTA）配体与两个三价act系元素（Am 3+和Pu 3+）的络合，并结合计算方法扩展了X射线吸收精细结构。这两个阳离子的络合过程类似于先前用相似离子半径的镧系元素（III）观察到的络合过程。络合反应发生在不同的步骤中，最终形成（1：1）络合物[（An（III）DOTA）（H 2 O）] -，其中阳离子与环的氮原子，四个羧酸酯臂和一个水分子键合，以完成配位球。An（III）-DOTA络合物的形成要快于等效离子半径的Ln（III）-DOTA系统。此外，发现An–N距离略短于Ln–N距离。理论计算表明，DOTA对Am与Nd的亲和力略高，这与氧和氮原子引起的配体对金属电荷的贡献略有增加有关。
• Co-Crystallization of Plutonium(III) and Plutonium(IV) Diglycolamides with Pu(III) and Pu(IV) Hexanitrato Anions: A Route to Redox Variants of [Pu^III,IV(DGA)₃][Pu^III,IV(NO₃)₆]_x
  作者：Brian M. Rotermund、Joseph M. Sperling、Gregory P. Horne、Nicholas B. Beck、Hannah B. Wineinger、Zhuanling Bai、Cristian Celis-Barros、Daniela Gomez Martinez、Thomas E. Albrecht-Schönzart

  DOI：10.1021/acs.inorgchem.3c01590

  日期：2023.8.14

  nuclear fuel reprocessing technologies, has been crystallized with plutonium, a transuranic actinide that has multiple accessible oxidation states. Two plutonium TMDGA complexes, [PuIII(TMDGA)3][PuIII(NO3)6] and[PuIV(TMDGA)3][PuIV(NO3)6]2·0.75MeOH, were crystallized through solvent diffusion of a reaction mixture containing plutonium(III) nitrate and TMDGA. The sample was then partially oxidized by air

  N,N,N',N'-四甲基二甘醇酰胺 (TMDGA) 是二甘醇酰胺萃取剂的甲基化变体，被提议作为先进废旧核燃料后处理技术中的锔保留试剂，已与钚（一种超铀锕系元素）一起结晶，钚具有多种可接近性氧化态。通过溶剂扩散结晶得到两种钚TMDGA配合物[Pu III (TMDGA) 3 ][Pu III (NO 3 ) 6 ]和[Pu IV (TMDGA) 3 ][Pu IV (NO 3 ) 6 ] 2 ·0.75MeOH含有硝酸钚(III)和TMDGA的反应混合物。然后通过空气部分氧化样品以产生[Pu IV (TMDGA) 3 ][Pu IV (NO 3 ) 6 ] 2 ·0.75MeOH。单晶 X 射线衍射揭示了多核系统与六硝基阴离子物质一起结晶，从而深入了解难以捉摸的三价六硝基钚物质的首次固态分离。晶体学数据显示TMDGA金属中心周围的几何形状从Pu 3+到Pu 4+发生变化，对称性大约从C 4
• Periodic Trends within Actinyl(VI) Nitrates and Their Structures, Vibrational Spectra, and Electronic Properties
  作者：Matthieu Autillo、Richard E. Wilson、Monica Vasiliu、Gabriel F. de Melo、David A. Dixon

  DOI：10.1021/acs.inorgchem.2c02434

  日期：2022.10.3

  A series of actinyl(VI) nitrate salts of the form MAnO2(NO3)3, where M = NH4+ K+, Rb+, Cs+, and Me4N+ and AnO22+ = U, Np, Pu, and AnO2(NO3)2(H2O)2·H2O, and the uranyl tetranitrates M2UO2(NO3)4 have been synthesized from aqueous solution and their structures determined using single-crystal X-ray diffraction. Together, these complexes represent an isostructural series of actinide complexes among the

  一系列 MAnO 2 (NO 3 ) 3形式的actinyl(VI)硝酸盐，其中 M = NH 4 + K +、Rb +、Cs +和 Me 4 N +和 AnO 2 2+ = U、Np， Pu、AnO 2 (NO 3 ) 2 (H 2 O) 2 ·H 2 O、四硝酸铀酰 M 2 UO 2 (NO 3 ) 4已从水溶液合成，并使用单晶 X 射线衍射确定其结构。总之，这些配合物代表了用相同电荷补偿阳离子结晶的盐中的一系列同构锕系配合物，并且已经使用包括拉曼和傅里叶变换红外的振动光谱学进行了研究。介绍并讨论了这些配合物的结构性质及其振动光谱的周期性趋势，特别是在整个actinyl系列中观察到的O≡An≡O不对称拉伸频率的不变性。电子结构计算在各种理论水平上进行，以帮助解释振动数据并将数据趋势与这些分子的潜在电子特性相关联。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Np: TrU.C, 6, page 129 - 147
  作者：

  DOI：——

  日期：——
• Abraham, B. M.; Brody, B. B.; Davidson, N. R., in: G. T. Seaborg, J. J. Katz, W. H. Manning, The Transuranium Elements, Tl.1, New York-Toronto-London 1949, S.740/58
  作者：Abraham, B. M.、Brody, B. B.、Davidson, N. R.、Hagemann, F.、Karle, I.、et al.

  DOI：——

  日期：——