trans-{RuCl4(CH3CN)2} | 133932-80-6

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: trans-{RuCl4(CH3CN)2}
• CAS: 133932-80-6
• 化学式: C₄H₆Cl₄N₂Ru
• 分子量: 324.987
• InChiKey: OSSYFRZFXJKBRO-UHFFFAOYSA-J

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

• 作为产物：
  描述：

  以 乙醚 为溶剂， 生成 trans-{RuCl4(CH3CN)2} 、 hexachlororuthenate(IV)
  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

• Ru(CH3CN)3Cl3, preparation and use as a mediator for the electrooxidation of hydrocarbons
  作者：L Appelbaum、C Heinrichs、J Demtschuk、M Michman、M Oron、H.J Schäfer、H Schumann

  DOI：10.1016/s0022-328x(99)00532-x

  日期：1999.12

  Hydrogenation of ruthenium chloride in acetonitrile yields complexes of the type Ru(CH3CN)(n)Cl6-n of which three are isolated (n = 2, 3, 4). Their formation is traced by voltammetry. Ru(CH3CN)(2)Cl-4 and Ru(CH3CN)(3)Cl-3 have been characterized by single-crystal X-ray diffraction. Voltammetry shows that Ru(CH3CN)(3)Cl-3 acts as a mediator for oxidation of cyclohexene, methylcyclohexene, 1-tetralol and tetralin. Its role in tetralin oxidation is illustrated by preparative scale electrolysis. The compounds Ru(CH3CN)(2)Cl-4 and Ru(CH3CN)(4)Cl-2 did not react with any of the mentioned hydrocarbons. (C) 1999 Elsevier Science S.A. All rights reserved.