trans-[Ru(pyridine)₄(CN)₂] | 159473-02-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: trans-[Ru(pyridine)₄(CN)₂]
• 英文别名: trans-[Ru(py)₄(CN)₂]
• CAS: 159473-02-6
• 化学式: C₂₂H₂₀N₆Ru
• 分子量: 469.511
• InChiKey: DSDCGWBCXGDURH-UHFFFAOYSA-N

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：
  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：

  trans-[Ru(pyridine)₄(CN)₂] 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 以 氯仿 为溶剂， 以92%的产率得到
  参考文献：
  名称：

  Heterometallic cyanide-bridged complexes containing RhIRuIIRhI triad: NMR data on exchange reactions and ligand effect transmission

  摘要：

  Trans-[RuPy4(CN)(2) cleaves chloro-rhodium bridges in rhodium(I) binuclear complexes, [Rh(CO)(2)Cl](2), [Rh(Cod)Cl](2), and [(Cod)RhCl2Rh(CO)(2)] yielding heterometallic triad complexes, [(CO)(2)ClRh(NC)RuPy4(CN)RhCl(CO)(2)] (I), [(Cod)ClRh(NC)RuPy4(CN)RhCl(Cod)] (II), and [(Cod)ClRh(NC)RuPy4(CN)RhCl(CO)(2)] (III), respectively. In solutions, III coexists with equilibrium amounts of I and II in the near-binomial proportions. Under action of [Rh(CO)(2)Cl](2), II transforms into I with parallel formation of [Rh(Cod)Cl](2). Ligand effect transmission along the L-Rh-NC-Ru-CN-Rh-L' chain is studied by H-1 and C-13 NMR. Chemical shifts delta H-1 and delta C-13 of Ru-bound Py ligands are sensitive to the nature of Rh-bound ligands. Values of delta H-1 and delta C-13 of Cod and C-13 of CO ligands are sensitive to the ligands at the remote end of the L-Rh-NC-Ru-CN-RhL' chain. Reaction of trans-[RuPy4(CN)(2)] with Rh-2(OAc)(4) yields an apparently linear polymer [-Rh(OAc)(4)Rh-NCRuPy4CN-]. Upon action of [Rh(CO)(2)Cl](2), the polymer decomposes yielding I and Rh-2(OAc)(4). X-ray structure data for I are given. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.04.028
• 作为产物：
  描述：

  吡啶 、 potassium cyanide 、 trans-dichlorotetrakis(pyridine-N)ruthenium(II) 以 吡啶 、 水 为溶剂， 以89%的产率得到trans-[Ru(pyridine)₄(CN)₂]
  参考文献：
  名称：

  Coe, Benjamin J.; Meyer, Thomas J.; White, Peter S., Inorganic Chemistry, 1995, vol. 34, # 3, p. 593 - 602

  摘要：

  DOI：

文献信息

• Fine Tuning of the Electronic Coupling between Metal Centers in Cyano-Bridged Mixed-Valent Trinuclear Complexes
  作者：Pablo Alborés、Leonardo D. Slep、Thomas Weyhermüller、Luis M. Baraldo

  DOI：10.1021/ic0493649

  日期：2004.10.1

  report the synthesis, characterization, and spectroscopic properties of a family of trinuclear cyano-bridged mixed-valent compounds, trans-[Ru(II)L(4)[NCFe(III)(CN)(5)](2)](4-), trans-[Ru(II)L(4)[CNFe(III)(CN)(5)](2)](4-), and cis-[Ru(II)(bpy)(2)[NCFe(III)(CN)(5)](2)](4-) (L = pyridine, 4-tert-butylpyridine, and 4-methoxypyridine). Tetraphenylphosphonium salts of complexes trans-[Ru(II)L(4)[NCFe(III)(CN)(5)](2)](4-)

  我们报告的合成，表征，和光谱性质的三核氰基桥联的混合价化合物，反-[Ru（II）L（4）[NCFe（III）（CN）（5）]（2）] （4-），反式-[Ru（II）L（4）[CNFe（III）（CN）（5）]（2）]（4-）和顺式[Ru（II）（bpy）（2 ）[NCFe（III）（CN）（5）]（2）]（4-）（L ＝吡啶，4-叔丁基吡啶和4-甲氧基吡啶）。反式-[Ru（II）L（4）[NCFe（III）（CN）（5）]（2）]（4-）的配合物的四苯基phosph盐在空间中结晶C2和P2（1）/ c分别表示金属单元的线性排列和赤道配体的几乎完全黯淡的构型。在光谱的NIR区域中观察到所有化合物的强谱带（ε约为2000-9000 M（-1）cm（-1）），在分离的结构单元中不存在，并高度依赖溶剂。在简化的三中心模型的背景下，我们将其分配为从Ru（II）到末端Fe（III）部分的金属到金属的电
• Emissive cyanide-bridged bimetallic compounds as building blocks for polymeric antennae
  作者：Alejandro Cadranel、Bruno M. Aramburu Trošelj、Shiori Yamazaki、Pablo Alborés、Valeria D. Kleiman、Luis M. Baraldo

  DOI：10.1039/c3dt51164b

  日期：——

  A series of cyanide-bridged bimetallic compounds of the general formula [Ru(L)(bpy)(μ-NC)(M)]2−/−/2+ (L = tpy, 2,2′-6′,2′′-terpyridine, or tpm, tris(1-pyrazolyl)methane, bpy = 2,2′-bipyridine, M = RuII(CN)5, OsIII(CN)5, OsII(CN)5, RuII(py)4(CN), py = pyridine) have been synthesized and fully characterized. Most of them present MLCT emission (λ = 690–730 nm, Φ = 10−3–10−4) and their photophysical properties resemble the ones of the respective mononuclear Ru(L)(bpy) species. The exception is when M is OsIII(CN)5, where an intramolecular electron transfer quenching mechanism is proposed. The conditions that should be met for avoiding the reductive or oxidative quenching of the excited state are also discussed.

  一系列通式为[Ru(L)(bpy)(μ-NC)(M)]2-/-2+（L = tpy，2,2′-6′,2′′-三吡啶，或 tpm、M=RuII(CN)5、OsIII(CN)5、OsII(CN)5、RuII(py)4(CN)，py=吡啶）进行了合成和全面表征。它们大多具有 MLCT 发射（λ = 690-730 纳米，Φ = 10-3-10-4），其光物理性质与相应的单核 Ru(L)(bpy) 物种相似。但当 M 为 OsIII(CN)5 时例外，有人提出了分子内电子转移淬灭机制。此外，还讨论了避免激发态还原或氧化淬灭应满足的条件。
• Long Range Metal‐Metal Interactions Along Fe−NC−Ru−CN−Fe Chains
  作者：Tianlu Sheng、Heinrich Vahrenkamp

  DOI：10.1002/ejic.200300656

  日期：2004.3

  Trinuclear complexes with linear FeII−NC−RuII−CN−FeII arrays were obtained by attachment of FeCp(dppe) units to the cyanoruthenium complexes trans-[Ru(CN)2(Py)4] (Py = pyridine, 4-methylpyridine, 4-ethylpyridine) . From their cyclic voltammograms it can be concluded that there are long-range metal−metal interactions between their external iron centers. Partial oxidation led to the isolation of the corresponding

  具有线性 FeII-NC-RuII-CN-FeII 阵列的三核配合物是通过将 FeCp(dppe) 单元连接到氰基钌配合物反式-[Ru(CN)2(Py)4]（Py = 吡啶，4-甲基吡啶， 4-乙基吡啶）。从它们的循环伏安图可以得出结论，它们的外部铁中心之间存在长程金属-金属相互作用。部分氧化导致相应的混合价 FeII-NC-RuII-CN-FeIII 复合物的分离。对于这些，从 NIR 光谱中的宽 MMCT 波段可以明显看出长距离金属 - 金属相互作用。MMCT 特性通过使用 Hush 形式主义的分析进行量化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Vibronic Coupling in Dicyano-Complex-Bridged Mixed-Valence Complexes. Relaxation of Vibronic Constraints in Systems with Degenerate Bridging-Ligand and Electron-Transfer Excited States
  作者：Ariel V. Macatangay、John F. Endicott

  DOI：10.1021/ic9900713

  日期：2000.2.1

  D-[(NC)M(CN)]-A, systems is treated as the consequence of the perturbational mixing of the "local", D(NC)M and M(CN)A, vibronic interactions. If M is an electron-transfer acceptor, then the nuclear coordinates are assumed to be configured so that bQN is larger for D(NC)M but very small (bQN approximately 0) for M(CN)A. When the vertical energies of the corresponding charge-transfer transitions, EDM and

  在由反式Ru（py）4（CN）2和顺式Os（bpy）2桥接的混合价Ru（NH3）5（2 +，3 +）配合物中发现了强烈的近红外（NIR）吸收带（CN）2，对于波长分别为1,000和1,300 nm的波段，ε约为1.5 x 10（3）cm（-1），而deltav1 / 2约为5 x 10（3）cm（-1）。NIR跃迁暗示了混合价络合物中中等强度电子耦合的大量复合常数（分别为64和175）。这与由M（MCL）（CN）2+络合物（MCL =四氮杂大环配体）桥接的Ru（NH3）5（2 +，3 +）偶合的弱禁止电子偶合形成鲜明对比（Macatangay; J. Phys.Chem.1998，102，7537）。一个简单的摄动理论论点被用来解释这种相反的行为。氰化物桥联之间的电子耦合 供体-受体对，D-（CN-）-A，改变桥联配体的性质。这样的系统由“振动”模型描述，其中电子矩阵元素HDA是桥联配体的核坐标QN的函数：HDA
• Binuclear rhodium organometallic complexes as catalysts of the liquid-phase 1-octene oxidation
  作者：Yu. B. Trach、O. I. Makota、L. V. Bulgakova、T. G. Cherkasova、A. B. Nikol’skii、Yu. S. Varshavskii

  DOI：10.1134/s1070363210070273

  日期：2010.7

  mononuclear rhodium organometallic complexes are active catalysts of the 1-octene oxidation by molecular oxygen. In this communication we present preliminary results of studying catalytic properties of complexes containing several metal centers, namely binuclear complexes of rhodium (+1), rhodium (+3), iridium (+1), palladium (+2), and triad complexes containing the ruthenium (+2) complex trans-[Ru(py)4(CN)2]

  分子氧催化烯烃液相氧化反应属于最有前途的有机合成过程，是众多出版物的主题（例如，参见 [1-3]）。我们最近表明 [4] 单核铑有机金属配合物是分子氧氧化 1-辛烯的活性催化剂。在本次通讯中，我们介绍了研究含有几个金属中心的配合物的催化性能的初步结果，即铑 (+1)、铑 (+3)、铱 (+1)、钯 (+2) 的双核配合物和含有钌 (+2) 配合物反式-[Ru(py)4(CN)2] 作为中心单元，铑 (+1) 或钯 (+2) 配合物作为末端片段。