[Ru(2,2';6',2''-terpyridine)(6,6'-dichloro-2,2'-bipyridine)(Cl)]Cl | 136710-58-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Ru(2,2';6',2''-terpyridine)(6,6'-dichloro-2,2'-bipyridine)(Cl)]Cl
• 英文别名: {Ru(II)(2,2':6',2''-terpyridine)(6,6'-dichloro-2,2'bipyridine)Cl{Cl；[Ru(terpy)(dcbpy)(Cl)]Cl
• CAS: 136710-58-2
• 化学式: C₂₅H₁₇Cl₃N₅Ru*Cl
• 分子量: 630.325
• InChiKey: YJLZPUCOGQAZAT-UHFFFAOYSA-L

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：

  [Ru(2,2';6',2''-terpyridine)(6,6'-dichloro-2,2'-bipyridine)(Cl)]Cl 以 水 、 丙酮 为溶剂， 生成 {Ru(II)(2,2':6',2''-terpyridine)(6,6'-dichloro-2,2'bipyridine)(H2O)}{ClO4}2
  参考文献：
  名称：

  用稳定的配体调节钌-氧配合物的反应性。6,6'-二氯-2,2'-联吡啶的钌（IV）-氧配合物作为化学计量和催化有机氧化的活性氧化剂

  摘要：

  [Ru II（terpy）（dcbipy）（H 2 O）] 2+（terpy = 2,2'：6'，2''-terpyridine; dcbipy = 6,6'-dichloro-2,2的合成与表征描述了'-联吡啶。用Ce IV氧化该络合物得到[Ru IV（terpy）（dcbipy）O] 2+，分离为浅绿色的高氯酸盐。Ru IV O络合物是顺磁性的（µ eff = 2.83），并且在780 cm –1处表现出Ru O拉伸。它是一种强氧化剂，E °（Ru IV –Ru III）= 1.13 V vs .。pH值为1.0的饱和甘汞电极，可以选择性地氧化金刚烷的C–H叔键。对Ru IV O氧化烯烃的机理进行了研究和讨论。络合物[Ru II（terpy）（dcbipy）（H 2 O）] 2+是用于叔丁基氢过氧化物氧化饱和烷烃的稳健催化剂。

  DOI：

  10.1039/dt9910001901
• 作为产物：
  描述：

  Ru(tpy)(Cl)₃ 、 6,6’-二氯-2,2’-联吡啶 在 HCl 作用下， 以 乙二醇 为溶剂， 生成 [Ru(2,2';6',2''-terpyridine)(6,6'-dichloro-2,2'-bipyridine)(Cl)]Cl
  参考文献：
  名称：

  用稳定的配体调节钌-氧配合物的反应性。6,6'-二氯-2,2'-联吡啶的钌（IV）-氧配合物作为化学计量和催化有机氧化的活性氧化剂

  摘要：

  [Ru II（terpy）（dcbipy）（H 2 O）] 2+（terpy = 2,2'：6'，2''-terpyridine; dcbipy = 6,6'-dichloro-2,2的合成与表征描述了'-联吡啶。用Ce IV氧化该络合物得到[Ru IV（terpy）（dcbipy）O] 2+，分离为浅绿色的高氯酸盐。Ru IV O络合物是顺磁性的（µ eff = 2.83），并且在780 cm –1处表现出Ru O拉伸。它是一种强氧化剂，E °（Ru IV –Ru III）= 1.13 V vs .。pH值为1.0的饱和甘汞电极，可以选择性地氧化金刚烷的C–H叔键。对Ru IV O氧化烯烃的机理进行了研究和讨论。络合物[Ru II（terpy）（dcbipy）（H 2 O）] 2+是用于叔丁基氢过氧化物氧化饱和烷烃的稳健催化剂。

  DOI：

  10.1039/dt9910001901

文献信息

• Spontaneous Formation in the Dark, and Visible Light-Induced Cleavage, of a Ru–S Bond in Water: A Thermodynamic and Kinetic Study
  作者：Azadeh Bahreman、Bart Limburg、Maxime A. Siegler、Elisabeth Bouwman、Sylvestre Bonnet

  DOI：10.1021/ic401105v

  日期：2013.8.19

  In this work the thermal and photochemical reactivity of a series of ruthenium complexes [Ru(terpy) (N-N)(L)](X)(2) (terpy = 2,2';6',2 ''-terpyridine, L = 2-(methylthio)ethanol (Hmte) or water, and X is Cl- or PF6-) with four different bidentate chelates N-N = bpy (2,2'-bipyridine), biq (2,2'-biquinoline), dcbpy (6,6'-dichloro-2,2'-bipyridine), or dmbpy (6,6'-dimethyl-2,2'-bipyridine), is described. For each chelate N-N the thermodynamic constant of the dark equilibrium between the aqua- and Hmte- complexes, the Hmte photosubstitution quantum yield, and the rate constants of the thermal interconversion between the aqua and Hmte complexes were measured at room temperature. By changing the steric hindrance and electronic properties of the spectator N-N ligand along the series bpy, biq, dcbpy, dmbpy the dark reactivity clearly shifts from a nonlabile equilibrium with N-N = bpy to a very labile thermal equilibrium with N-N = dmbpy. According to variable-temperature rate constant measurements in the dark near pH = 7 the activation enthalpies for the thermal substitution of H2O by Hmte are comparable for all ruthenium complexes, whereas the activation entropies are negative for bpy and biq, and positive for dcbpy and dmbpy complexes. These data are indicative of a change in the substitution mechanism, being interchange associative with nonhindered or poorly hindered chelates (bpy, biq), and interchange dissociative for more bulky ligands (dcbpy, dmbpy). For the most labile dmbpy system, the thermal equilibrium is too fast to allow significant modification of the composition of the mixture using light, and for the nonhindered bpy complex the photosubstitution of Hmte by H2O is possible but thermal binding of Hmte to the aqua complex does not occur at room temperature. By contrast, with N- N = biq or dcbpy the thermodynamic and kinetic parameters describing the formation and breakage of the Ru-S bond lie in a range where the bond forms spontaneously in the dark, but is efficiently cleaved under light irradiation. Thus, the ratio between the aqua and Hmte complex in solution can be efficiently controlled at room temperature using visible light irradiation.