cis,trans,cis-[Ru(NC5H4NNC6H4-m-Cl)2Cl2] | 210179-01-4

• 英文名称: cis,trans,cis-[Ru(NC5H4NNC6H4-m-Cl)2Cl2]
• CAS: 210179-01-4；325148-44-5；648928-39-6
• 化学式: C₂₂H₁₆Cl₄N₆Ru
• 分子量: 607.291
• InChiKey: URFGPOQAZGIKAH-IVZMTRENSA-L

计算性质

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

反应信息

• 作为反应物：
  描述：

  cis,trans,cis-[Ru(NC5H4NNC6H4-m-Cl)2Cl2] 、 水杨酸 在 AgNO₃ 、 NaOH 作用下， 以 乙醇 为溶剂， 生成
  参考文献：
  名称：

  Mononuclear and dinuclear ruthenium(II)/(III) salicylates incorporating azoimine functionalities as ancillary ligands. Synthesis, spectroscopic and electron-transfer properties†

  摘要：

  我们合成了含有偶氮亚胺基氮吡啶配体 L 的水杨酸钌配合物，其类型为 [RuII(L)2(salicylate)] 1-5 [L = NC5H4NNC6H4(R)，R = H、m-Me/Cl 或 p-Me/Cl]，并对其光谱电化学方面进行了研究。这些配合物系统地表现出两个 1e- 氧化过程和两个 2e- 氧化过程，以及四个连续的单电子还原过程。对每个氧化步骤的电子和 EPR 光谱研究表明，最初的单电子氧化过程相当于将钌（II）中心立体氧化成钌（III），即 [RuIII(L)2(水杨酸盐)]+++-5+++。第二个氧化步骤相当于将 1++-5++ 中配位的水杨酸分子氧化为钌(III)-水杨酸半醌阳离子自由基 [RuIII(L)2(水杨酸)]2+E。电生成的钌(III)同系物（1++-5+++）显示出与畸变八面体配合物相对应的菱形 EPR 光谱。电生成的水杨酸半醌基[RuIII(L)2(水杨酸)]2+E 经历了一个自由基重组过程，从而形成了反铁磁耦合的二聚物[(L)2RuIII(X)RuIII(L)2]4+F[(X = -O2C(O)C6H4C6H4(O)CO2-]。接下来的两个 2e- 氧化过程与二聚物[(L)2RuIII(X′)RuIII(L)2]4+G[(X′=-O2C(O)C6H3C6H3(O)CO2-]的桥基氧化有关，然后是金属中心的氧化，即[(L)2RuIV(X′)RuIV(L)2]6+H。络合物 1-5 被 HNO3 化学氧化后会直接形成二聚络合物 G。这些配合物在紫外-可见光区域显示出强烈的电荷转移带，并在从 1-5 到 1++-5++ 再到 F 再到 G 的过程中发生了合理的蓝移。

  DOI：

  10.1039/b100163i
• 作为产物：
  描述：

  2-(3-chlorophenylazo)pyridine 、 {Ru(CS)Cl(PPh3)2}2(μ-Cl)2 以 甲醇 为溶剂， 生成 cis,trans,cis-[Ru(NC5H4NNC6H4-m-Cl)2Cl2]
  参考文献：
  名称：

  A facile and preferential synthesis of the complexes, cis-trans-cis-RuII [NC5H4NNC6H4(R)]2 (R = H, o-Me/Cl, m-Me/Cl, p-Me/Cl) Synthesis, spectroscopic characterization and electron-transfer properties

  摘要：

  A group of seven complexes of the type ctc-(RuL2Cl2)-L-II (2a-2g) (L = NC5H4-N=N-C6H5(R), R = H, o-Me/Cl, m-Me/Cl, p-Me/Cl and ctc = cic-trans-cis with respect to chlorides, pyridine and azo nitrogens, respectively) have been synthesized and characterized. The complexes are diamagnetic (Ru-II, t(2g)(6), S = 0) and electrically neutral. The molecular geometry of the complexes (2) in solution has been established by H-1 NMR spectroscopy. They exhibit a strong metal to ligand charge-transfer band in the range 582-603 nm and intra ligand pi-pi* transition near 320 nm. In acetonitrile solution the complexes display reversible ruthenium(II) reversible arrow ruthenium(III) oxidation couples in the range 1.02 --> 1.36 V vs SCE. Two successive quasi-reversible ligand reductions are observed for each complex in the ranges -0.42 --> -0.60 V and -0.68 --> -0.85 V vs SCE, respectively. The complexes 2a and 2e have been oxidized tb the corresponding trivalent species (3a and 3e) by using HNO3 as oxidizing agent and isolated in solid state as perchlorate salts. Complexes are one-electron paramagnets (Ru-III, t(2g)(5), S = 1/2) and show 1:1 conductivity in acetonitrile solution. The presence of perchlorate counter ion in the complexes has been evidenced by the strong infrared bands near 1100 and 600 cm(-1). Complexes exhibit a strong ligand to metal charge-transfer band near 530 nm and intra ligand pi-pi* transition near 370 nm. In glassy condition (77 K) complexes display rhombic EPR spectra corresponding to the distorted octahedral geometry. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(97)00512-3

文献信息

• Ruthenium terpyridine complexes incorporating azo-imine based ancillary ligands. Synthesis, crystal structure, spectroelectrochemical properties and solution reactivities †
  作者：Biplab Mondal、Mrinalini G. Walawalkar、Goutam Kumar Lahiri

  DOI：10.1039/b005789o

  日期：——

  Ruthenium terpyridine complexes of the type [RuII(trpy)(L)(X)][ClO4]n1–15 [trpy = 2,2′∶6,2′′-terpyridine; L = NC5H4NNC6H4(R), R = H, m-Me, m-Cl, p-Me or p-Cl; X = Cl−, n = 1 (1–5); H2O, n = 2 (6–10) or OH−, n = 1 (11–15)] have been synthesized. The single crystal structures of 1 and 6 were determined. Complex 4 develops in two possible isomeric forms whereas all other complexes stabilise preferentially

  [Ru II（trpy）（L）（X）] [ClO 4 ] n 1–15 [trpy = 2,2'∶6,2''-叔吡啶；L = NC 5 H 4 N NC 6 H 4（R），R = H，m -Me，m -Cl，p -Me或p -Cl；X =氯- ，Ñ  = 1（1-5）;高氧2，Ñ  = 2（6-10）或OH - ，Ñ  = 1（11-15）]已被合成。确定了1和6的单晶结构。配合物4以两种可能的异构形式发展，而所有其他配合物优先以一种异构形式稳定。该复合物在500 nm附近表现出很强的MLCT谱带，并且配体紫外线区域中的基于过渡的过渡。1–5在600 nm附近的77 K处显示中等强度的发射。这氯代（1–5）和羟基（11–15）配合物显示钌（III）–钌（II）对以及3至4个连续的单电子配体基于减少量。水复合物（6–10）表现出可逆的2e − / 2H +单步氧化作用在[Ru II（trpy）（L）（H
• A new class of sulfur bridged ruthenium–molybdenum complexes, (L)2RuII(μ-S)2MoIV(OH)2 [L=NC5H4N=NC6H4(R), R=H, o-Me/Cl, m-Me/Cl]. Synthesis, spectroscopic and electron-transfer properties
  作者：Ramapati Samanta、Pradip Munshi、Bidyut Kumar Santra、Goutam Kumar Lahiri

  DOI：10.1016/s0277-5387(98)00385-4

  日期：1999.2

  H 4 N=NC 6 H 4 (R), R=H, o -Me/Cl, m -Me/Cl; ctc = cis–trans–cis with respect to chlorides, pyridine and azo nitrogens respectively] in MeOH–H 2 O (1:1) resulted in a group of stable sulfur bridged ruthenium–molybdenum complexes of the type (L) 2 Ru II (μ-S) 2 Mo IV (OH) 2 (2a–2e). In complexes 2 the terminal MoS bonds of the Mo VI S 4 2− unit get hydroxylated and the molybdenum ion is reduced from

  摘要（NH 4）2 Mo VI S 4与络合物ctc -Ru II（L）2 Cl 2（1a-1e）[L = NC 5 H 4 N = NC 6 H 4（R），R = H，o -Me / Cl，m -Me / Cl; ctc =分别相对于氯化物，吡啶和偶氮氮的顺式-反式-顺式] [MeOH–H 2 O（1：1），生成一组稳定的硫桥接的钌-钼络合物，类型为（L）2 Ru II （μ-S）2 Mo IV（OH）2（2a-2e）。在配合物2中，Mo VI S 4 2-单元的末端MoS键被羟基化，并且钼离子从MoS 4 2-的起始Mo VI还原为最终产物2中的Mo IV。 RuL 2 S 2片段中2的顺式（分别针对硫，吡啶和偶氮基）构型已通过1 H NMR光谱确定。在二氯甲烷溶液中，络合物2在550 nm附近表现出很强的dπ（Ru II）→Lπ* MLCT跃迁，在500 nm附近有很强的硫到钼的LMCT跃迁，而在UV区则有内配体π–π