3,5-bis[bis(1,4,5-trimethyilmidazol-2-yl)-methoxymethyl]pyrazolate | 1032544-26-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 3,5-bis[bis(1,4,5-trimethyilmidazol-2-yl)-methoxymethyl]pyrazolate
• 英文别名: 3,5-bis[bis-(1,4,5-trimethylimidazol-2-yl)methoxymethyl]pyrazole；2-[methoxy-[3-[methoxy-bis(1,4,5-trimethylimidazol-2-yl)methyl]-1H-pyrazol-5-yl]-(1,4,5-trimethylimidazol-2-yl)methyl]-1,4,5-trimethylimidazole
• CAS: 1032544-26-5
• 化学式: C₃₁H₄₄N₁₀O₂
• 分子量: 588.756
• InChiKey: MZGDQLADDRYWJF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  43
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  118
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,5-bis[bis(1,4,5-trimethyilmidazol-2-yl)-methoxymethyl]pyrazolate 、 ruthenium(III) chloride trihydrate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.17h， 以91%的产率得到{[Ru^IIICl₂]₂(μ-bimp)(μ-Cl)}
  参考文献：
  名称：

  Powerful Bis-facially Pyrazolate-Bridged Dinuclear Ruthenium Epoxidation Catalyst

  摘要：

  A new bis-facial dinuclear ruthenium complex, {[Ru-II(bpy)](2)(mu-bimp)(mu-Cl)}(2+), 2(2+), containing a hexadentate pyrazolate-bridging ligand (Hbimp) and bpy as auxiliary ligands has been synthesized and fully characterized in solution by spectrometric, spectroscopic, and electrochemical techniques. The new compound has been tested with regard to its capacity to oxidize water and alkenes. The in situ generated bis-aqua complex, {[Ru-II(bpy)(H2O)](2)(mu-bimp)}(3+), 3(3+), is an excellent catalyst for the epoxidation of a wide range of alkenes. High turnover numbers (TN), up to 1900, and turnover frequencies (TOF), up to 73 min(-1), are achieved using Phi as oxidant. Moreover, 3(3+) presents an outstanding stereospecificity for both cis and trans olefins toward the formation of their corresponding epoxides due to specific interactions transmitted by its ligand scaffold. A mechanistic analysis of the epoxidation process has been performed based on density functional theory (DFT) calculations in order to better understand the putative cooperative effects within this dinuclear catalyst.

  DOI：

  10.1021/acs.inorgchem.5b00641

文献信息

• New Pyrazole-Based Ligands with Two Tripodal Binding Pockets: Potential Scaffolds for Metallobiosite Modeling
  作者：Holger Müller、Bernhard Bauer-Siebenlist、Edit Csapo、Sebastian Dechert、Etelka Farkas、Franc Meyer

  DOI：10.1021/ic800248b

  日期：2008.6.1

  dissociated into their bimetallic constituents. The solid state structures observed for the oligonuclear complexes 4- 8 are reminiscent of the coordination motifs previously found for related mononuclear complexes based on tripodal tris(imidazolyl)methane, which corroborates the description of HL1-HL3 as novel binucleating versions of such tris(imidazolyl)methane ligands.

  报道了基于桥联吡唑酸酯并附加了螯合臂的一组新的生物启发的双核配体支架HL1-HL3的合成。配体提供类似于三（咪唑基）甲烷基序的两个结合区室，倾向于用作面部三齿配位帽。在Ni2 +和Zn2 +存在下的HL1电位滴定揭示了水溶液中金属：配体比率为1：1的物质的形成，NiII系统的UV-vis数据表明[L12Ni2] 2+与（NiN6）的配合物发色团是在适当的pH条件下形成的。相反，三镍（II）配合物[L2 2Ni3（NO3）4（MeOH）2]（4）和[L2 2Ni3CL2（MeOH）4] CL2（5）可以从MeOH溶液中获得并进行结晶表征。实际上，中心NiII离子实现了配体的预期三脚架（N3）结合模式，但是抗衡阴离子或MeOH溶剂分子导致外部NiII离子的N供体分支之一解离，并在结合Ni的MeOH和吡唑酸酯-N之间形成分子内的H键。还获得了三个CuI络合物[L3 2Cu4X2]（PF6）2的X射线晶体结构，其中X