| 90821-19-5

• CAS: 90821-19-5
• 化学式: C₃₂H₃₂Cl₂N₄Ru
• 分子量: 644.609
• InChiKey: LUYAIVVUWALUFB-SCVZJUFRSA-L

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：

  以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Amide Formation from Aldimine and Water Promoted by Coordinated Metal Redox. Chemistry of a Family of Isomeric RuII(diimine)2Cl2, RuIII(diimine)2Cl2+, and RuIII(diimine)(amide-imine)Cl2 Complexes

  摘要：

  The relevant N,N-coordinating ligands are RN=(H)-C(H)=NR (general abbreviation D, specific abbreviations D-1 and D-2 for R = cyclohexyl and p-tolyl, respectively) and [RN=C(H)-C(=O)-NR](-) (abbreviations A, A(1), A(2). Oxidation of cis- and trans-(RuD2Cl2)-D-II by aqueous cerium(IV) (H2O2 can also be used for trans-RuD2Cl2) affords in excellent yield the amide complexes cis- and trans-Ru(III)DACl(2) with retention of parental isomeric structure. Spectral and magnetic characterization data of the complexes are reported along with the X-ray structures of cis-RuD12Cl2 . PhMe and cis-RuD(1)A(1)Cl(2) . CH2Cl2. The ruthenium(III)-ruthenium(II) couples of the complexes follow E(1/2) systematics (other things remaining the same in each case): geometry, cis > trans; ligand, D > A; substituent, p-tolyl > cyclohexyl. The (RuD2Cl2+)-D-III moiety has been electrogenerated in solution, and cis- [(RuD2Cl2)-D-III-Cl-1]ClO4 has been isolated and characterized in the pure state. The conversion RuD2Cl2 --> RuDACl(2) actually occurs via RuD2Cl2+, which reacts with water, affording the amide complex. The reaction is first order with respect to both RuD2Cl2+ and H2O, and the activation parameters are Delta h(double dagger) = 12.5 kcal mol(-1) and Delta S-double dagger = -29.8 eu in the case of trans-(RuD2Cl2)-Cl-2. It is proposed that the water molecule adds to the azomethine function and the a-hydroxy amine function of the adduct is rapidly oxidized via an induced electron transfer pathway. The net reactions are as follows: RuD2Cl2 --> RuD2Cl2+ + e; RuD2Cl2+ + H2O --> RuDACl(2) + 2e + 3H(+). A crucial reaction condition appears to be the easy accessibility of two oxidation states of the metal ion related by facile transfer of one electron, the higher oxidation state being sufficiently polarizing to induce water binding at the aldimine site. Crystal data for the complexes are as follows: cis-(RuD2Cl2)-Cl-1 . PhME, crystal system monoclinic, space group P2(1)/c, a = 14.808(6) Angstrom, b = 19.442(7) Angstrom, c = 13.989(6) Angstrom, beta = 117.18(3)degrees, V = 3583(2) A(3), Z = 4, R = 3.70%, R(w) = 4.31%; cis-RuD(1)A(1)Cl(2) . CH2Cl2, crystal system monoclinic, space group P2(1)/c, a = 11.295(4) Angstrom, b = 27.064(14) Angstrom, c = 12.064(4) Angstrom, beta = 107.52(2)degrees, V = 3517(2) A(3), Z = 4, R = 6.53%, R(w) = 6.95%.

  DOI：

  10.1021/ic00116a025
• 作为产物：
  描述：

  以 邻二甲苯 为溶剂， 生成
  参考文献：
  名称：

  1,4-二氮杂丁二烯配体与顺式 RuCl2 部分的钌配合物用于醇的催化无受体脱氢：化学非无害配体参与的 DFT 证据。

  摘要：

  报道了通过二氮杂丁二烯配位钌化合物将伯醇无受体脱氢偶联（ADC）为酯。使用不同的 1,4-二氮杂丁二烯在 56 °C 的丙酮中处理 cis-Ru(dmso)4Cl2 [p-XC6H4N[双键，长度为中划线]C(H)(H)C[双键，长度为中划线]C(H)(H)C[双键，长度为中划线] m-破折号]NC6H4X-p；X = H、CH3、OCH3 和 Cl；缩写为 DAB-X]，给出反式-Ru[κ2-N,N-DAB-X]2Cl2 作为取代的动力学产物。将这些产物在邻二甲苯中于 144 °C 加热，得到热力学上有利的顺式-Ru[κ2-N,N-DAB-X]2Cl2 异构体。电子结构计算证实顺式非对映异构体具有更高的稳定性。每对几何异构体的分子结构均已通过 X 射线衍射分析确定。配合物的循环伏安实验显示，与 SCE 相比，氧化反应和还原反应分别在 0.50 至 0.93 V 和 -0.76 至 -1.24

  DOI：

  10.1039/d3ra04750d

文献信息

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

  DOI：——

  日期：——