trans-{N(C4H9)4}{RuCl4(CH3CN)2} | 137355-20-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: trans-{N(C4H9)4}{RuCl4(CH3CN)2}
• 英文别名: trans-(Bu4N)[RuCl4(CH3CN)2]
• CAS: 137355-20-5
• 化学式: C₄H₆Cl₄N₂Ru*C₁₆H₃₆N
• 分子量: 567.456
• InChiKey: CWPNSXVNBLFWIB-UHFFFAOYSA-J

反应信息

• 作为反应物：
  描述：

  trans-{N(C4H9)4}{RuCl4(CH3CN)2} 以 二氯甲烷 、 乙腈 为溶剂， 生成 mer-{N(C4H9)4}{RuCl3(CH3CN)3}
  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
• 作为产物：
  描述：

  cis-[Ru(NO)Cl4(CH3CN)](1-) 以 乙腈 为溶剂， 以58%的产率得到trans-{N(C4H9)4}{RuCl4(CH3CN)2}
  参考文献：
  名称：

  Successive Chemical Reactions Accompanying a One-Electron Oxidation of a {MNO}⁶-Type Nitrosyl Complex, Pentachloro(nitrosyl)ruthenate(2−), and a Characterization of the Product Species

  摘要：

  A one-electron oxidation species of the title complex, [Ru(NO)Cl5]−({RuNO}5-type nitrosyl complex), converted into cis-[Ru(NO)Cl4(CH3CN)]−({RuNO}6-type nitrosyl complex) at low temperature (5 °C) in the dark. The product species could be isolated and characterized. An X-ray structure determination showed a remarkably short N–O bond distance of the Ru–NO moiety: l(N–O) = 0.998 Å, l(Ru–N) = 1.787(5) Å, ∠Ru–N–O = 175.1(6)°. Under room light at 25 °C, the complex underwent a facile nitrosyl photoelimination to give trans-[RuCl4(CH3CN)2]−, the structure of which was also established. During the course of the reactions, two other unidentified species were confirmed to exist by cyclic voltammetry.

  DOI：

  10.1246/bcsj.68.2897