[tris(μ-chloro)bis((triphos)ruthenium(II))] chloride | 103500-17-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: [tris(μ-chloro)bis((triphos)ruthenium(II))] chloride
• 英文别名: {Ru2(μ-Cl)3(triphos)2}Cl；[Ru2(μ-Cl)3(κ3-1,1,1-tris(diphenylphosphinomethyl)ethane)2]Cl；[Ru2(μ-Cl)3(κ3-triphos)2]Cl；[Ru2(μ-Cl)3(MeC(CH2PPh2)3)2]Cl；[Ru2(μ-Cl)3(triphos)2]Cl；[Ru2(triphos)Cl3]
• CAS: 103500-17-0
• 化学式: C₈₂H₇₈Cl₃P₆Ru₂*Cl
• 分子量: 1593.32
• InChiKey: PTAULWYONPXYOU-UHFFFAOYSA-M

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

• 作为反应物：
  描述：

  [tris(μ-chloro)bis((triphos)ruthenium(II))] chloride 、 silver trifluoromethanesulfonate 在 MeCN 作用下， 以 乙腈 为溶剂， 以92%的产率得到[(MeC(CH2PPh2)3)Ru(acetonitrile)3](CF3SO3)2
  参考文献：
  名称：

  Rhodes, Larry F.; Sorato, Carla; Venanzi, Luigi M., Inorganic Chemistry, 1988, vol. 27, # 4, p. 604 - 610

  摘要：

  DOI：
• 作为产物：
  描述：

  1,1,1-三(二苯基膦甲基)乙烷 、 dichlorotetrakis(dimethylsulfoxide)ruthenium 以 氯仿 为溶剂， 以75%的产率得到[tris(μ-chloro)bis((triphos)ruthenium(II))] chloride
  参考文献：
  名称：

  用于自组装反应的带有封端配体的新型 RuII-dmso 前体的合成和结构和光谱表征

  摘要：

  这项工作的目的是制备新的、易于制造的、具有面部几何形状的八面体 Ru II 前体，用于自组装反应。我们选择 dmso 作为离去基团和 1,4,7-三硫杂环壬烷 ([9]aneS 3 )、三(吡唑基)甲烷 [CH(pz) 3 , pz = pyrazol-1-yl] 或三磷 [CH 3 C (CH 2 PPh 2 ) 3 ]作为封面配体(fcl)。我们在此描述了三种新型双阳离子 Ru II 配合物（作为三氟甲磺酸盐）的制备和结构表征，其类型为 fac[Ru(fcl)(solv) 3 ] 2 + ，即 fac-[Ru([9]aneS 3 )( dmso-O)(dmso-S) 2 ] 2 + (3b)，其在溶液中与连接异构体 fac-[Ru([9]aneS 3 )(dmso-O) 2 (dmso-S)] 2 + (3a)、fac[Ru{CH(pz) 3 }(dmso-O)(dmso-S) 2 ]

  DOI：

  10.1002/ejic.200400717
• 作为试剂：
  描述：

  α-甲基-γ-丁内酯 在 [tris(μ-chloro)bis((triphos)ruthenium(II))] chloride potassium tert-butylate 、 氢气 作用下， 以 甲醇 为溶剂， 100.0 ℃ 、4.0 MPa 条件下， 反应 13.0h， 以39.7%的产率得到1,4-戊二醇
  参考文献：
  名称：

  METHOD FOR PRODUCING ALCOHOL BY HYDROGENATING LACTONE OR CARBOXYLIC ACID ESTER IN LIQUID PHASE

  摘要：

  公开号：

  EP2141142B1

文献信息

• [Ru(triphos)(CH₃CN)₃](OTf)₂ as a homogeneous catalyst for the hydrogenation of biomass derived 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium
  作者：Elnaz Latifi、Austin D. Marchese、Margaret C. W. Hulls、Dmitriy V. Soldatov、Marcel Schlaf

  DOI：10.1039/c7gc01956d

  日期：——

  5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium at temperatures between 150 and 200 °C realizing up to 96% combined yields of 2,5-hexanediol and 2,5-dimethyl-tetrahydrofuran with the product distribution being sensitive to the amount of acid co-catalyst (HOTf) present. For the furan, the reaction pathway is through an acid-catalyzed hydrolysis to the dione rather than direct hydrogenation

  络合物[Ru（triphos）（CH 3 CN）3 ]（OTf）2是一种有效的催化剂，可在150至200°C的温度下，在含水酸性介质中将2,5-己二酮和2,5-二甲基呋喃加氢，实现2,96-己二醇和2,5的合计产率高达96％ -二甲基-四氢呋喃，产物分布对存在的酸助催化剂（HOTf）的数量敏感。对于呋喃，反应途径是通过酸催化的水解成二酮，而不是环的直接氢化。对二酮的氢化反应显示出对氢压力的一级依赖性，这是通过在温度和压力下（150°C下为1.38–6.90 MPa）直接测量氢的吸收率来确定的，并且假定该氢可通过[Ru]的氢杂化活化作用进行操作。 （H）x（triphos）（Y）y ] n+（Y =溶剂，水，抗衡离子）物种通过腈配体的损失和氢化原位形成。在水中，催化剂通过二聚反应失活为[Ru 2（μ-OH） 3（triphos） 2 ]（OTf）。
• Germa‐ <i>closo</i> ‐dodecaborate: An Ambident and Flexible Coordinating Ligand
  作者：Jörg‐Alexander Dimmer、Lars Wesemann

  DOI：10.1002/ejic.201000857

  日期：2011.1

  nucleophilicity of the germanium cluster vertex in the iron derivative 3 is high enough to react with [Mo(CO)5(thf)] to give the bimetallic complex [(triphos)Fe(GeB11H11)(MoCO)5] (5), which contains an ambident coordinating germaborate moiety. The new compounds have been characterized by single-crystal X-ray diffraction and elemental analysis. Soluble complexes were also investigated by 1H, 11B, and 31P NMR spectroscopy

  遵循简单的一锅程序，从 FeBr2 和三磷 [MeC(CH2PPh2)3] 或二聚体 [Ru2(μ-Cl)3(triphos)2]Cl 与亲核试剂 [Bu3MeN]2[GeB11H11] 开始反应在乙腈中，两性离子乙腈加合物 [M(GeB11H11)(triphos)(MeCN)2] [M = Fe (1), M = Ru (2)] 以良好的产率分离。通过简单的 η1(Ge) 到 η3(B–H) 重排，1 和 2 可以转化为 [M(GeB11H11)(triphos)] [M = Fe (3), M = Ru (4)]。铁衍生物 3 中锗簇顶点的亲核性足够高，可以与 [Mo(CO)5(thf)] 反应生成双金属配合物 [(triphos)Fe(GeB11H11)(MoCO)5] (5)，它包含一个环境协调的锗硼酸盐部分。新化合物已通过单晶 X 射线衍射和元素分析进行​​表征。1H、11B、和
• Bonding modes of stanna-closo-dodecaborate: η¹(Sn) to η³(BH) rearrangement reactions in zwitterionic stanna-closo-dodecaborate ruthenium complexes
  作者：Torben Gädt、Klaus Eichele、Lars Wesemann

  DOI：10.1039/b517138e

  日期：——

  Reaction of the stanna-closo-dodecaborate salt [Bu3MeN]2[SnB11H11] with the dimeric ruthenium complex [Ru2(µ-Cl)3(triphos)2]Cl (triphos = MeC(CH2PPh2)3}) in refluxing acetonitrile yields the zwitterionic compound [Ru(SnB11H11)(MeCN)2(triphos)] (4) which has been characterized by single-crystal X-ray diffraction analysis and solid-state NMR spectroscopy. Refluxing the zwitterion 4 in acetone leads to an η1(Sn) to η3(BH) rearrangement with formation of [Ru(SnB11H11)(triphos)] (5) whose structure has been confirmed by X-ray diffraction and multinuclear NMR spectroscopy in solution and in the solid state. Furthermore, two isomeric zwitterions fac- and mer-[Ru(SnB11H11)(dppb)(MeCN)3] (6a, 6b) and their rearrangement reactions as well as their NMR properties are described.

  在回流乙腈中，[Bu3MeN]2[SnB11H11]与二聚钌复合物[Ru2(µ-)Cl)3(triphos)2]Cl（triphos = MeC(CH2PPh2)3}）在回流乙腈中生成齐聚物[Ru(SnB11H11)(MeCN)2(triphos)]（4）。在丙酮中回流齐聚物 4 会导致δ-1(Sn)到δ-3(BH)重排，形成[Ru(SnB11H11)(triphos)](5)，其结构已在溶液和固态中通过 X 射线衍射和多核核磁共振光谱得到证实。此外，还介绍了 fac- 和 mer-[Ru(SnB11H11)(dppb)(MeCN)3] (6a, 6b) 两种异构齐聚物及其重排反应和核磁共振特性。
• Reactivity and Catalytic Activity of a Robust Ruthenium(II)−Triphos Complex
  作者：Adrian B. Chaplin、Paul J. Dyson

  DOI：10.1021/ic701773a

  日期：2008.1.1

  The ruthenium(II)-triphos acetatc, complex [RuCl(OAc)(k(3)-triphos)] (triphos = (PPh2CH2)(3)CMe) has been found to be an active catalyst precursor for the hydrogenation of 1-alkenes under relatively mild conditions (5-50 bar H-2, 50 degrees C). In contrast to related triphenylphosphine complexes, [RuCl(OAc)(k(3)-triphos)] is much less air sensitive and 14 high catalytic activities were achieved when catalyst samples were prepared without exclusion of air or moisture. Substitution of the acetatc, ligand can be effected by treatment of acid, affording [Ru-2(mu-Cl)(3)(k(3)-triphos)(2)]Cl and [RuCl(k(3)-triphos)](2)(BF4)(2) with aqueous HCl and [Et2OH]BF4, respectively, or by heating with dmpm in the presence of [NH4]PF6, resulting in formation of [RuCl(k(2)-dMPM)(k(3)-triphos)]PF6 (dmpm = PMe(2)CH(2)PMe2). A hydride complex, [RuHCl (k(3)-triphos)], formed by acetato-mediated heterolytic cleavage of dihydrogen is proposed as the active catalytic species. An inner-sphere, monohydride mechanism is suggested for the catalytic cycle, with chloro and triphos ligands playing a spectator role. These mechanistic proposals are consistent with reactivity studies carried out on [RuCl(OAc) (k(3)-triphos)] and [RuH(OAc)(k(3)-triphos)] and supported by a computational analysis. The solid-state structures of [RuCl(OAc)(k(3)-triphos)], [RuCl(k(3)-triphos)](2)(BF4)(2), and [RUCl(k(2)-dmpm)(k(3)-triphos)]PF6 have been established by X-ray diffraction.