{Ru(CH3CO2)2(py)4} | 15691-86-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: {Ru(CH3CO2)2(py)4}
• 英文别名: pyridine;ruthenium(2+);diacetate
• CAS: 15691-86-8
• 化学式: C₂₄H₂₆N₄O₄Ru
• 分子量: 535.565
• InChiKey: MIVXBNOZKNYVKP-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.84
• 重原子数：
  33
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  132
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  {Ru(CH3CO2)2(py)4} 以 neat (no solvent) 为溶剂， 生成 {Ru(CH3CO2)2(py)2}
  参考文献：
  名称：

  新的羧酸钌络合物

  摘要：

  三氯化磷与羧酸酸酐的混合物水合钌的相互作用，得到式[Ru中的结晶复合物2（OCOR）4 CL]，（RME等，Ñ PR），其中，所述钌原子具有II和的形式氧化态三，这些配合物在300-100°K的温度范围内具有很高的磁矩，并且似乎是要制备的第一种钌的无自旋配合物。描述了其他不太明确的羧酸钌盐。

  DOI：

  10.1016/0022-1902(66)80118-5
• 作为产物：
  描述：

  [Ru3(μ3-O)(μ-O2CMe)6(pyridine)3]PF6 在 Zn 作用下， 以 吡啶 、 溶剂黄146 为溶剂， 以68%的产率得到{Ru(CH3CO2)2(py)4}
  参考文献：
  名称：

  Comparison between Iron and Ruthenium Reagents Mediating Gif^IV-Type Oxygenation of Cyclohexane

  摘要：

  A ruthenium-based version of Barton's Gif(IV)-type system (Ru-cat/Zn/O-2 in pyridine/acetic acid) for the selective oxygenation of cycloalkanes has been studied in detail for the first time using a range of analytical techniques. The system, based on the use of the triruthenium complex [Ru3O(O2CCH3)(6)(py)(3)] in the presence of zinc powder in aerated pyridine/acetic acid (10:1 v/v), affords yields of cyclohexanone (main product) and cyclohexanol from cyclohexane comparable to that of the well-studied iron system based on the use of [Fe3O(O2CCH3)(6)(py)(3)]. py but with a lower selectivity for the ketone product. The time taken for the appearance and distribution of the -one/-ol products is different for the two metals and also depends on the efficiency of stirring of the zinc powder. The differing -one/-ol ratios and their times of appearance have been correlated with competing reactions on the intermediate cyclohexylhydroperoxide, most likely generated via oxygen- and carbon-centered radical chemistry. The appearance of cyclohexanol much earlier in the reaction for the ruthenium-based system has been traced to a slower assembly reaction for ruthenium to form the species responsible for the ketonization step, which allows production of alcohol via;zinc reduction of cyclohexylhydroperoxide to compete successfully. Extensive investigations into the nature of the metal species present during turnover, using cyclic voltammetry, H-1 NMR and UV-vis spectroscopy, show that for either system the divalent monomeric complex trans-[M(O2CCH3)(2)-(py)(4)] (M = Ru or Fe) is the major species present during the appearance of ketone product. Use of trans-[Fe-(O2CCH3)(2)(py)(4)] as the precursor reagent results in the highest Gif(IV) activity (conversion yield) toward cyclohexane oxygenation. It is concluded that formation of sec-alkylhydroperoxides in addition to monomeric divalent complexes such as trans-[M(O2CCH3)(2)(py)(4)]. (M = Fe or Ru) are key processes central to the mechanism of the Gif oxygenation process toward ring hydrocarbons. The combination Fe(II)/ROOH is considered responsible for the formation of ketone (and some alcohol), most likely via Haber-Weiss chemistry, in competition with formation of alcohol via Zn reduction of ROOH.

  DOI：

  10.1021/ic0001560

文献信息

• Reactions of tetra-µ-carboxylato-diruthenium(<scp>II</scp>,<scp>II</scp>) compounds. X-Ray crystal structures of Ru₂(µ-O₂CCF₃)₄(thf)₂, Ru₂(µ-O₂CR)₄(NO)₂(R = Et or CF₃), and {Na₃[Ru₂(µ-O₂CO)₄]·6H₂O}_n
  作者：Alan J. Lindsay、Geoffrey Wilkinson、Majid Motevalli、Michael B. Hursthouse

  DOI：10.1039/dt9870002723

  日期：——

  Improved procedures for the synthesis of the diruthenium(II) carboxylates, Ru2(µ-O2CR)4L2, and substitutions of either the bridged carboxylate or axial ligands (L) are described. Among new bridged compounds are the trifluoroacetate, Ru2(µ-O2CCF3)4, the carbonate, Na3[Ru2(µ-O2CO)4]·6H2O}n, and the triazenide, Ru2(µ-N3Ph2)4; adducts of the triazenide include the nitrosyl, Ru2(µ-N3Ph2)4(NO)2, the isocyanide

  为二钌（合成改进的程序II）羧酸盐，孺2（μ-O 2 CR）4大号2，并且或者桥接羧酸盐或轴向配体（L）的置换被描述。在新的桥联化合物中，有三氟乙酸盐Ru 2（µ-O 2 CCF 3）4，碳酸盐Na 3 [Ru 2（µ-O 2 CO）4 ]·6H 2 O} n和三叠氮化物Ru 2（µ-N 3 Ph 2）4; 所述triazenide的加合物包括亚硝酰，RU 2（μ-N 3博士2）4（NO）2，胩，RU 2（μ-N 3博士2）4（BU吨NC），和羰基的Ru 2（ μ-N 3博士2）4（CO）2。在某些情况下，羧酸盐与给体（如异氰化物，吡啶（py），膦或CO）的反应导致桥连裂解和产物，如反式-Ru（O 2 CR）2（py）4或Ru（O 2）CR）2（PPH 3）2（R = Me或CF 3），而与NO的反应中得到的反磁性加合物的Ru 2（μ-O 2 CR）4（NO）2。红外，nmr，esr和电
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Ru: SVol., 138, page 392 - 394
  作者：

  DOI：——

  日期：——