neptunoyl(V) perchlorate | 83477-23-0

• 英文名称: neptunoyl(V) perchlorate
• 英文别名: neptunyl(V) perchlorate；neptunyl perchlorate
• CAS: 83477-23-0
• 化学式: ClO₄*NpO₂
• 分子量: 368.498
• InChiKey: IWUQJWPCASFIQG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  neptunoyl(V) perchlorate 以 水 为溶剂， 生成 neptunyl perchlorate hexahydrate
  参考文献：
  名称：

  Bessonov, A. A.; Afonas'eva, T. V.; Krot, N. N., Radiokhimiya, 1991, vol. 33, p. 245 - 250

  摘要：

  DOI：
• 作为产物：
  描述：

  neptunyl(VI) perchlorate 在 C₃H₇CHNOH 作用下， 以 高氯酸 、 硝酸 为溶剂， 生成 neptunoyl(V) perchlorate
  参考文献：
  名称：

  Koltunov, V. S.; Mezhov, E. A.; Baranov, S. M., Radiochemistry, 2001, vol. 43, p. 342 - 345

  摘要：

  DOI：

文献信息

• Complexation of Np(<scp>v</scp>) with oxalate at 283–343 K: spectroscopic and microcalorimetric studies
  作者：Guoxin Tian、Linfeng Rao

  DOI：10.1039/c1dt11507c

  日期：——

  Thermodynamic parameters including the equilibrium constants and enthalpy of complexation of Np(V) with oxalate at variable temperatures (T = 283–343 K, ionic strength = 1.05 mol kg−1NaClO4) were determined by spectrophotometric and microcalorimetric titrations. The results show that the complexation of Np(V) with oxalate is moderately strong and becomes weaker at higher temperatures. The complexation is exothermic

  通过分光光度法和微量热滴定法测定了热力学参数，包括在可变温度（T = 283–343 K，离子强度= 1.05 mol kg -1 NaClO 4）下Np（V）与草酸盐的络合焓和焓。结果表明，Np（V）与草酸盐的络合强度中等，而在较高温度下变得较弱。在283 K至343 K的温度范围内，络合物是放热的，并且受焓（负）和熵（正）的驱动。随着温度的升高，络合物的焓和熵都增加（ΔH的负值变小，Δ小号变得更积极），对复合物有相反的影响。因为在焓（Δ增加ħ）超过了熵项（的Ť Δ小号），NP（络合V）与草酸变得在较高温度下弱。根据络合中涉及的离子溶剂化和氢键的能级，讨论了温度对络合的影响。
• Symmetry and optical spectra: a “silent” 1 : 2 Np(v)–oxydiacetate complex
  作者：Guoxin Tian、Linfeng Rao、Allen Oliver

  DOI：10.1039/b706825e

  日期：——

  The 1 : 2 Np(V)–oxydiacetate complex, NpO2(ODA)23−, identified by single-crystal X-ray diffractometry for the first time, is centrosymmetric around the Np atom so that the f–f transitions of Np(V) are forbidden, resulting in the “silence” of the absorption and diffuse reflectance spectra of this complex in solution and the solid state in the near-IR and visible regions.

  通过单晶 X 射线衍射仪首次确定了 1 : 2 Np（V）羰基二乙酸酯复合物 NpO2（ODA）23â，该复合物在 Np 原子周围呈中心对称，因此 Np（V）的 fâf 转变被禁止，导致该复合物在溶液和固体状态下的近红外和可见光区域的吸收和漫反射光谱â沉默。
• Complexation of Np(v) with N,N-dimethyl-3-oxa-glutaramic acid and related ligands: thermodynamics, optical properties and structural aspects
  作者：Linfeng Rao、Guoxin Tian、Simon J. Teat

  DOI：10.1039/b922851a

  日期：——

  Complexation of Np(V) with N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) was studied in comparison with its diamide analog, N,N,N′,N′-tetramethyl-3-oxa-glutaramide (TMOGA), and dicarboxylate analog, oxydiacetic acid (ODA). Thermodynamic parameters, including the stability constant and the enthalpy of complexation, were determined by spectrophotometry and calorimetry. Single-crystal structure of NpO2(H2O)(DMOGA)·H2O(c) was identified by X-ray diffractometry using synchrotron radiation. Like ODA and TMOGA, DMOGA forms a tridentate Np(V) complex, with three oxygen atoms coordinating to the linear NpO2+ moiety via the equatorial plane. The stability constants, enthalpy and entropy of complexation generally decrease in the order ODA > DMOGA > TMOGA, suggesting that the complexation is entropy driven and the substitution of a carboxylate group with an amide group reduces the strength of complexation with Np(V) due to the decrease in the entropy of complexation.

  研究了 Np(V) 与 N,N-二甲基-3-氧杂-谷氨酸 (DMOGA) 的络合，并将其与二酰胺类似物 N,N,N′,N′-四甲基-3-氧杂-谷酰胺 (TMOGA) 和二羧酸类似物氧二乙酸 (ODA) 进行了比较。通过分光光度法和量热法测定了包括稳定常数和络合焓在内的热力学参数。通过同步辐射 X 射线衍射仪确定了 NpO2(H2O)(DMOGA)- (c)的单晶结构。与 ODA 和 TMOGA 一样，DMOGA 形成了三叉Np(V) 复合物，三个氧原子通过赤道面与线性 + 分子配位。络合的稳定常数、焓和熵一般按照 ODA > DMOGA > TMOGA 的顺序降低，这表明络合是由熵驱动的，用酰胺基团取代羧酸基团会降低与 Np(V) 的络合强度，因为络合熵降低了。
• Crystal structure of a double Np(V) and Co(NH3) 6 3+ maleate, Co(NH3)6[NpO2(HL)2(H2O)3](HL)2?H2O [L = OOC(HC)2COO]
  作者：I. A. Charushnikova、N. N. Krot、Z. A. Starikova

  DOI：10.1007/s11137-005-0028-3

  日期：2004.11

  Crystal structure of a double Np(V) and Co(NH3) 6 3+ maleate Co(NH3)6[NpO2(HL)2(H2O)3](HL)2⋅H2O [L = OOC(HC)2COO] was studied. The crystal structure consists of complex anions [NpO2(HL)2(H2O)3]−, HL− anions, [Co(NH3)6]3+ cations, and water molecules of crystallization. Hydrogen bonds in which proton donors are water molecules and hexaamminecobalt cations link structural fragments to form a 3D network. The coordination polyhedra of the Np(V) atoms are pentagonal bipyramids whose equatorial planes are formed by oxygen atoms of two HL− anions and three water molecules. Four crystallographically independent maleate anions were identified in the structure. Two of these anions enter into the Np(V) surrounding, and their coordination capacity is 1.

  研究了双 Np(V) 和 Co(NH3) 6 3+ 马来酸盐 Co(NH3)6[NpO2(HL)2(H2O)3](HL)2⋅ [L = OOC(HC)2COO] 的晶体结构。晶体结构由复合阴离子[NpO2(HL)2( )3]-、HL-阴离子、[Co(NH3)6]3+阳离子和结晶水分子组成。质子供体为水分子和六氨合钴阳离子的氢键将结构片段连接起来，形成三维网络。Np(V) 原子的配位多面体为五角二棱柱，其赤道平面由两个 HL- 阴离子的氧原子和三个水分子构成。在该结构中发现了四个晶体学上独立的马来酸阴离子。其中两个阴离子进入 Np（V）原子周围，它们的配位能力为 1。
• Complexation-assisted reduction: complexes of glutaroimide-dioxime with tetravalent actinides (Np(<scp>iv</scp>) and Th(<scp>iv</scp>))
  作者：Zhicheng Zhang、Bernard F. Parker、Trevor D. Lohrey、Simon J. Teat、John Arnold、Linfeng Rao

  DOI：10.1039/c8dt01191e

  日期：——

  strong complexes with tetravalent Th(IV) and Np(IV) in aqueous solution. In conjunction with literature data on the complexation of glutaroimide-dioxime with other metal ions, it was found that the complexes become weaker as the effective charge density on the metal ions decreases: V5+ > Th4+ ≈ Fe3+ > UO22+ > Eu3+/Nd3+ > Cu2+ > Pb2+ > NpO2+ > Ca2+/Mg2+. In the glutaroimide-dioxime complexes with Th(IV)

  谷氨酰胺二肟与水溶液中的四价Th（IV）和Np（IV）形成强络合物。结合有关谷氨酰胺-二肟与其他金属离子络合的文献数据，发现随着金属离子上有效电荷密度的降低，络合物变得更弱：V 5+ > Th 4+ ≈Fe 3+ > UO 2 2+ > Eu 3+ / Nd 3+ > Cu 2+ > Pb 2+ > NpO 2 + > Ca 2+ / Mg 2+。在具有Th（IV）和Np（IV），酰亚胺基团的去质子化和肟基团中两个氢原子从氧到氮的重定位导致一个大的共轭体系（–O–N–C–N–C–N–O–）与通过中心酰亚胺氮原子和两个肟氧原子以三齿模式形成金属中心。由于具有Np（IV）的谷氨酰胺-二肟配合物的稳定性远高于具有Np（V）的戊二酰亚胺-二肟配合物，因此Np（V）/ Np（IV）对的氧化还原电势有望发生显着变化。结果，可以容易地从含有Np（V）的初始溶液中获得具有Np（IV）的谷氨酰胺-二肟复合物