trans-{RuCl2(C6H5CN)4} | 21503-87-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans-{RuCl2(C6H5CN)4}
• 英文别名: trans-[RuCl2(benzonitrile)4]；trans-[RuCl2(PhCN)4]；Benzonitrile;dichlororuthenium
• CAS: 21503-87-7；51014-03-0
• 化学式: C₂₈H₂₀Cl₂N₄Ru
• 分子量: 584.47
• InChiKey: QIYGNONDXNEXKQ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.61
• 重原子数：
  35
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  95.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-{RuCl2(C6H5CN)4} 、 1,4-bis(p-tolyl)-1,4-diaza-1,3-butadiene 以 四氢呋喃 为溶剂， 以76%的产率得到
  参考文献：
  名称：

  Dieck, Heindirk Tom; Kollvitz, Wolfgang; Kleinwächter, Ingo, Inorganic Chemistry, 1984, vol. 23, # 17, p. 2685 - 2691

  摘要：

  DOI：
• 作为产物：
  描述：

  mer-{N(C4H9)4}{RuCl3(C6H5CN)3} 、 苯甲腈 以 二氯甲烷 、 苯甲腈 为溶剂， 生成 trans-{RuCl2(C6H5CN)4}
  参考文献：
  名称：

  From [RuX₆] to [Ru(RCN)₆]: synthesis of mixed halide–nitrile complexes of ruthenium, and their spectroelectrochemical characterization in multiple oxidation states

  摘要：

  A complete series of benzonitrile- and acetonitrile-substituted ruthenium halide complexes [RuX6-n(RCN)n]z (n = 0-6), ranging stepwise from [RuX6]2- to [Ru(RCN)6]2+, has been prepared and characterized. Three series were established, having RCN/X = PhCN/Cl, PhCN/Br, and MeCN/Cl. The strategy of reductive substitution has been developed to prepare [RuX5(RCN)]2-, trans-[RuX4(RCN)2]-, mer-[RuX3(RCN)3] and trans-[RuX2(RCN)4] in turn from [RuX6]2- by systematic electrosynthetic routes, through detailed management of potential, temperature and RCN concentration. The monosubstituted pentahalogeno complexes are unstable and their preparation is only practicable via electrode-induced (Ru(IV) --> Ru(III)) halide displacement from [RuX6]2- at low temperature. At the divalent level, exhaustive substitution to form [RuX(RCN)5]+ and [Ru(RCN)6]2+ from [RuX2(RCN)4] required more forcing chemical conditions (Ag+ and CF3SO3H respectively). Voltammetric studies between -65 and 20-degrees-C confirm that the family of mixed halide-nitrile monomeric complexes is rich in redox chemistry, spanning oxidation states V to II. Under reversible conditions, the various metal-based electrode potentials for [RuX6-n(RCN)n]z are a linear function of the stoichiometry parameter, n, increasing by 0.45 Ru(V)-Ru(IV)) or 0.6 V (Ru(IV)-Ru(III) and Ru(III)-Ru(II)) per halide replace by nitrile. By use of spectroelectrogeneration techniques, the optical charge-transfer spectra for every available member of each family have been recorded in multiple oxidation levels, defining the states Ru(IV) for n = 0-2, Ru(III) for n = 0-5 and Ru(II) for n = 2-6. For the present complexes, there are unmistakable complementary progressions in the halide-to-metal (X --> Ru(III)) and metal-to-ligand (Ru(II) --> RCN) bands, in accord with the underlying trend in E1/2(Ru(III)-Ru(II)). These measurements present an unusual opportunity to document and analyse the characteristic trends in appearance and location of both ligand-to-metal (Ru(III)) and metal-to-ligand (Ru(II)) charge-transfer manifolds as a function of stoichiometry.

  DOI：

  10.1039/dt9910002401

文献信息

• Syntheses, Characterization, and Catalytic Ability in Alkane Oxygenation of Chloro(dimethyl sulfoxide)ruthenium(II) Complexes with Tris(2-pyridylmethyl)amine and Its Derivatives¹^,²
  作者：Motowo Yamaguchi、Hiroyuki Kousaka、Shinichi Izawa、Yoshiki Ichii、Takashi Kumano、Dai Masui、Takamichi Yamagishi

  DOI：10.1021/ic060722c

  日期：2006.10.1

  chloro(benzonitrile)ruthenium(II) complex, whereas the bis(benzonitrile)ruthenium(II) complex was obtained with BPG. The cis(Cl,N(amino))-[RuCl(TPA)(Me2SO)]+ complex is thermodynamically much less stable than the trans isomer and isomerizes in dimethyl sulfoxide at 65-100 degrees C. Oxygenation of alkanes catalyzed by these ruthenium(II) complexes has been examined. The chloro(dimethyl sulfoxide-kappaS)ruthenium(II)

  具有四齿配体的新钌（II）配合物，例如三（2-吡啶甲基）胺（TPA），三[2-（5-甲氧羰基）吡啶甲基]胺[5-（MeOCO）3-TPA]，三（2-已经制备了喹啉基甲基）胺（TQA）或双（2-吡啶基甲基）甘氨酸盐（BPG）。配体与[RuCl2（Me2SO）4]的反应产生了含有TPA或BPG的氯（二甲基亚砜-κS）钌（II）配合物的反式和顺式异构体的混合物，而反式（Cl，N对于5-（MeOCO）3 -TPA和TQA选择性地获得了（氨基））异构体。[RuCl（TPA）（Me2SO）] +配合物的反式和顺式异构体很容易通过分级重结晶分离。反式和顺式（Cl，N（氨基））-[RuCl（TPA）（Me2SO）] +配合物和反式（Cl，N（氨基））-[RuCl 5-（MeOCO）3- TPA}（Me2SO）] +络合物已通过X射线结构分析确定。TPA与[RuCl2（PhCN）4]的反应生成了氯（苄腈）
• Reactions of (polypyrazolylborato)(benzonitrile)rutheniums with terminal alkynes: Reactivity changeover by triethylamine toward arylalkyne polymerization or formation of (arylmethyl)(carbonyl) complexes
  作者：Masayoshi Onishi、Yasuhiro Arikawa、Mamoru Yamaguchi、Tomoe Nagano、Takayuki Inoue、Atsunobu Terasoba、Suguru Matsuo、Maki Nakagawa、Hiroyuki Kawano、Junko Nagaoka、Keisuke Umakoshi、Mutsuhisa Furukawa

  DOI：10.1016/j.jorganchem.2011.11.031

  日期：2012.3

  Reactions of (κ3-polypyrazolylborato)(benzonitrile)rutheniums [RuClB(4-Ypz)4}(PhCN)2] 4-Ypz; 4-bromo-1-pyrazolyl (Y = Br) and 1-pyrazolyl (Y = H) groups} with terminal alkynes were studied. For the reactions with arylalkynes HCC(aryl) in the presence of NEt3, (arylmethyl)(carbonyl)rutheniums [RuCH2(aryl)}B(4-Ypz)4}(CO)(PhCN)] were yielded, indicating alkyne CC bond cleavage, whereas in the absence

  （反应的κ 3 -polypyrazolylborato）（苄腈）合钌将[RuCl B（4- YPZ）4 }（PHCN）2 ] 4- YPZ; 研究了带有末端炔烃的4-溴-1-吡唑基（Y = Br）和1-吡唑基（Y = H）基团。对于在NEt 3存在下与芳基炔烃HC C（芳基）进行反应的情况，是（芳基甲基）（羰基）钌[Ru CH 2（芳基）} B（4-Ypz）4 }（CO）（PhCN）]产生炔烃C C键断裂，而在不存在NEt 3的情况下，进行芳基炔烃聚合而不是形成（芳基甲基）钌。合理归因的反应机理表明，亚乙烯基中间体“ Ru CCH（芳基）”。
• Mono-, di- and poly-nuclear transition-metal complexes of a bis(tridentate) ligand: towards p-phenylenediamine-bridged co-ordination polymers
  作者：Alan Hazell、Christine J. McKenzie、Lars Preuss Nielsen

  DOI：10.1039/a800602d

  日期：——

  prototype example of each class of complex has been characterized. In [ZnCl2(2,4-tpbd)] the 1,4-tpbd is co-ordinated via only one of its tridentate ends. Both ends of 1,4-tpbd are bound in a dipalladium complex. [Pd2Cl2(1,4-tpbd)][PdCl3(dmso)]2. This structure constitutes the first example of a crystal structure of the counter anion [PdCl3(dmso)]–. The chloride salt of the [Pd2Cl2(tpbd)]2+ cation has

  双（三齿）配体Ñ，Ñ，Ñ '，Ñ ' N'-四（2-吡啶基甲基）苯-1,4-二胺（1,4- TPBD）是在该单官能，二-和多-核过渡可以制备金属配合物和双配位配合物。每类复合物的原型实例已被表征。在[ZnCl 2（2,4-tpbd）]中，1,4-tpbd仅通过其三齿末端之一进行配位。1,4-tpbd的两端都结合在二铝配合物中。[Pd 2 Cl 2（1,4-tpbd）] [PdCl 3（dmso）] 2。该结构构成了抗衡阴离子[PdCl]的晶体结构的第一个例子。3（dmso）] –。还分离出了[Pd 2 Cl 2（tpbd）] 2+阳离子的氯化物盐。在[ZnCl 2（1,4-tpbd）]和[Pd 2 Cl 2（tpbd）] 2+的结构中，都有明显的1,4-tpbd苯连接基的醌型特征。化合物[Ru（1,4-tpbd） 2 ] [PF 6 ] 2是双配位络合物的例子。每个配体的一个三齿末端与钌配位（
• The four-electron oxidation of meso-octaethylporphyrinogen via a metal-mediated dealkylation process: formation of [RuL(PhCN)2][H2L = 5,15-dihydro-5,5,10,15,15,20-hexaethylporphyrin]
  作者：Umberto Piarulli、Carlo Floriani、Angiola Chiesi-Villa、Corrado Rizzoli

  DOI：10.1039/c39940000895

  日期：——

  A four-electron oxidation of meso-octaethylporphyrinogen (H4L′) involving the dealkylation of two meso carbons has been observed in the reaction between [Ru(Cl)2(PhCN)4] and [Li4L′(THF)4] leading to [RuL(PhCN)2] which contains two hemiporphyrin fragments joined by two sp3 carbons, as shown by an X-ray analysis.

  在[Ru(Cl)2(PhCN)4]和[Li4L′(THF)4]的反应中，已观察到中间八乙基卟啉原（H4L′）的四电子氧化，其中涉及两个中间碳的脱烷基化，最终生成[RuL(PhCN)2]，其中包含两个由两个sp3碳连接起来的半卟啉片段，如X射线分析所示。
• Syntheses and characterization of new (pyrazolato)(pyrazole) rutheniums with κ3-polypyrazolylborates: Halogeno-anion binding through the tris(pyrazole) moiety
  作者：Masayoshi Onishi、Mamoru Yamaguchi、Shiho Kumagae、Hiroyuki Kawano、Yasuhiro Arikawa

  DOI：10.1016/j.ica.2005.08.005

  日期：2006.2

  (Polypyrazolylborato)(benzonitrile) ruthenium(II) complexes [RuClBR(pz)(3)}(PhCN)(2)] (R = pz, H; pz = pyrazol-1-yl), prepared from trans-[RuCl2(PhCN)(4)] and K[BR(pz)(3)], were allowed to react with potassium 3,5-dimethyl-substituted polypyrazolylborate salt K[BH(3,5-Me(2)pz)(3)], and gave (pyrazolato)(pyrazole) species of [RuBR(pz)(3)) (3,5-Me(2)pz)(3,5-Me(2)pzH)(2)] [R = pz (1), H (2)}, respectively. Upon protonation with HBF4 (Et2O), the species 1 was converted to a fairly stable tris(pyrazole) derivative [RuB(pz)(4)}(3,5-Me(2)pzH)(3)]BF4 (3), which worked as a novel halogeno-anion receptor. Moreover, the complex [RuCl2(PhCN)(4)] was treated with K[BH(3,5-Me-2-4-BrPZ)(3)] in the presence of 3,5-dimethyl-4-bromopyrazole, 3,5-Me-2-4-BrpzH, to afford [RuBH(3,5-Me-2-4-Brpz)(3)}(3,5-Me-2-4-Brpz)(3,5-Me2-4-BrpzH)(2)] and [RuBH(3,5-Me-2-4-Brpz)(3)}(3,5-Me-2-4-Brpz)(3,5-Me-2-4-BrpzH)(PhCN)]. Single-crystal X-ray structural analyses were carried out for 1, 3 center dot CHCl3, [Ru[B(pz)(4)}(3,5-Me(2)PzH)(2)(OH2)]O3SC6H4CH3 center dot CH3OH, and [RuClB(pz)(4))(3,5-Me(2)pzH)(2)]center dot CHCl3. (c) 2005 Elsevier B.V. All rights reserved.