hexa-aquairidium(III) | 61003-29-0

• 英文名称: hexa-aquairidium(III)
• 英文别名: hexaaquairidium(III)；iridium(3+);hexahydrate
• CAS: 61003-29-0
• 化学式: H₁₂IrO₆
• 分子量: 300.312
• InChiKey: VMNMDWXWAHLJOB-UHFFFAOYSA-N

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：

  hexa-aquairidium(III) 以 水 为溶剂， 生成 pentahydroxy(oxo)iridium(IX)
  参考文献：
  名称：

  The Slowest Water Exchange at a Homoleptic Mononuclear Metal Center:  Variable-Temperature and Variable-Pressure ¹⁷O NMR Study on [Ir(H₂O)₆]³⁺

  摘要：

  The rate constants and activation parameters for water exchange on hexaaqua and monohydroxy pentaaqua iridium(III) have been determined by O-17 NMR spectroscopy as a function of temperature (358-406 K) and pressure (0.1-210 MPa) at several acidities (0.5-5.0 m). Noncoordinating trifluoromethanesulfonate (CF3SO3-) was used as the counterion. The observed rate constant was of the form k = k(1) + k(2)/[H+], where the subscripts 1 and 2 refer to the exchange pathways on [Ir(H2O)(6)](3+) and [Ir(H2O)(5)(OH)](2+), respectively. The kinetic parameters obtained are summarized as follows: k(1)(298) = (1.1 +/- 0.1) X 10(-10) s(-1), Delta H-1(double dagger) = 130.5 +/- 0.6 kJ mol(-1), Delta S-1(double dagger) = +2.1 +/- 1.7 J K-1 mol(-1), and Delta V-1(double dagger) = -5.7 +/- 0.5 cm(3) mol(-1); k(2)(298) = (1.4 +/- 0.6) X 10(-11) m s(-1), Delta H-2(double dagger) = 138.5 +/- 4.5 W mol(-1), Delta S-2(double dagger) = +11.5 +/- 11.6 J K-1 mol(-1), and Delta V-2(double dagger) = -0.2 +/- 0.8 cm(3) mol(-1). The value obtained for k(1)(298) corresponds to a residence time of ca. 300 years. The pK(a)(298) and the volume change Delta V-a(0) associated with the first hydrolysis of [Ir(H2O)(6)](3+) were determined by potentiometric and high-pressure spectrophotometric methods to be 4.45 +/- 0.03 and -1.5 +/- 0.3 cm(3) mol(-1), respectively. Utilizing the relation k(2) = k(OH)K(a1), values for the first-order rate constant and the corresponding activation volume for [Ir(H2O)(5)(OH)](2+) were estimated to be k(OH)(298) = 5.6 x 10(-7) s(-1) and Delta V-OH(double dagger) = +1.3 cm(3) mol(-1), respectively. These data are supportive of an associative interchange (I-a) mechanism for water exchange on [Ir(H2O)(6)](3+), but of an interchange (I) mechanism on the deprotonated species [Ir(H2O)(5)(OH)](2+). These mechanistic results have also been compared to those reported for other trivalent metal ions.

  DOI：

  10.1021/ja954071n
• 作为产物：
  描述：

  iridium(III) hydroxide hydrate 以 高氯酸 为溶剂， 生成 hexa-aquairidium(III)
  参考文献：
  名称：

  Castillo-Blum, Sylvia E.; Richens, David T.; Sykes, A. Geoffrey, Inorganic Chemistry, 1989, vol. 28, # 5, p. 954 - 960

  摘要：

  DOI：

文献信息

• Kinetic studies of the complexation of oxalate to hexa-aquairidium(III)
  作者：Marion R. McMahon、Alison McKenzie、David T. Richens

  DOI：10.1039/dt9880000711

  日期：——

  A kinetic study of the oxalate anation of hexa-aquairidium(III) perchlorate in HClO4–NaClO4 solution, I= 1.5 mol dm–3(NaClO4), is reported. The acidity dependence ([H+]= 0.14 – 1.00 mol dm–3) is consistent with the existence of two parallel pathways involving anation by both H2C2O4 and HC2O4–. Rate constants (25 °C) and activation parameters for the two paths are: H2C2O4, k1=(1.3 ± 0.2)× 10–5 dm3 mol–1

  报道了在HClO 4 -NaClO 4溶液中，I = 1.5 mol dm -3（NaClO 4）的高氯酸六水合铱（III）的草酸盐阴离子化反应的动力学研究。酸度依赖性（[H + ] = 0.14 – 1.00 mol dm –3）与存在两个平行的途径有关，该途径涉及H 2 C 2 O 4和HC 2 O 4 –的阴离子化。两条路径的速率常数（25°C）和激活参数为：H 2 C 2 O 4，k 1=（1.3±0.2）×10 –5 dm 3 mol –1 s –1，ΔH 1 ‡ = 73.1±4.6 kJ mol –1，ΔS 1 ‡ = –94.1±13.9 JK –1 mol –1；和HC 2 O 4 –，k 2 =（7.2±1.2）×10 –6 s –1，ΔH 2 ‡ = 108±7 kJ mol –1，ΔS 2 ‡ = + 20.3±22.4 JK –1 mol – 1。HC的离子对缔合2
• Combined Experimental and Theoretical Approach to the Study of Structure and Dynamics of the Most Inert Aqua Ion [Ir(H₂O)₆]³⁺ in Aqueous Solution
  作者：Flora Carrera、Francisco Torrico、David T. Richens、Adela Muñoz-Páez、José M. Martínez、Rafael R. Pappalardo、Enrique Sánchez Marcos

  DOI：10.1021/jp0713716

  日期：2007.7.1

  LIII-edge X-ray absorption near-edge structure (XANES) spectra of three concentrations of [Ir(H2O)6]3+ in perchloric acid media were measured. To carry out classical MD simulations of the aqua ion in water, a new set of first-principles Ir-H2O intermolecular potentials, based on the hydrated ion concept, has been developed. Structural, dynamics, and energetic properties have been obtained from the analysis

  通过使用X-理论的组合实验理论方法首次实现了对六水合铱（III）[Ir（H2O）6] 3+在水溶液中的定量水合结构的定量测定，水溶液是已知的最惰性的水合离子。射线吸收光谱法和分子动力学（MD）模拟。三种浓度的[Ir（ ）6]的Ir LIII边缘扩展X射线吸收精细结构（EXAFS）光谱和LI-，LII-和LIII边缘X射线吸收近边缘结构（XANES）光谱测量了高氯酸介质中的3+。为了对水中的水合离子进行经典的MD模拟，基于水合离子的概念，开发了一组新的第一性原理Ir- 分子间电势。通过对生成的统计轨迹进行分析，获得了结构，动力学和能量特性。Ir-O径向分布函数在2.04 +/- 0.01和4.05 +/- 0.05 A处分别显示出两个明确定义的峰，分别对应于第一和第二水合壳；MD模拟很好地再现了水中的水基离子的基本频率，其动态特性与其他六水合三价离子的实验值相似。特别注意的是第二水合壳的实验测定。已经发现，与基于Ir3
• Substitution inertness of [Ir(H2O)6]3+
  作者：Silvia E. Castillo-Blum、A.Geoffrey Sykes、Heinz Gamsjäger

  DOI：10.1016/s0277-5387(00)81244-9

  日期：1987.1

  Ligand substitution properties of the recently characterized pale-yellow [Ir(H2O)6]3+ ion in perchlorate solutions, have been investigated. At 120°C in sealed tubes observations on the exchange with H218O are impaired by a spurious oxidation to purple Ir(IV). Over extended periods at 40°C the ion has been shown to be extremely inert, and the rate constants for substitution of Cl− into [Ir(H2O)6]3+ is

  研究了高氯酸盐溶液中最近表征的浅黄色[Ir（H2O）6] 3+离子的配体取代性能。在120°C的密闭管中，与H218O的交换观察因杂化氧化为紫色Ir（IV）而受到损害。在40°C下的长时间中，离子已显示出极高的惰性，并且将Cl-取代为[Ir（ ）6] 3+的速率常数估计为<2×10-9 M-1 S -1。
• Sanchez-Ortiz, Vanesaa A.; Martinez-Jardines, L. Gerardo; Castillo-Blum, Silvia E., Journal of the Chemical Society, Dalton Transactions, 1998, # 4, p. 663 - 666
  作者：Sanchez-Ortiz, Vanesaa A.、Martinez-Jardines, L. Gerardo、Castillo-Blum, Silvia E.、Sykes, A. Geoffrey

  DOI：——

  日期：——
• Rodgers, Kenton R.; Gamsjäger, Heinz; Murmann, R. Kent, Inorganic Chemistry, 1989, vol. 28, # 2, p. 379 - 381
  作者：Rodgers, Kenton R.、Gamsjäger, Heinz、Murmann, R. Kent

  DOI：——

  日期：——