[Cu(pmap)]B(C6F5)4 | 1004985-32-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Cu(pmap)]B(C6F5)4
• CAS: 1004985-32-3
• 化学式: C₂₀H₂₂CuN₄*C₂₄BF₂₀
• 分子量: 1061.01
• InChiKey: FTVSDHFCWQPMOS-UHFFFAOYSA-N

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：

  5,10,15,20-(tetra-2,6-difluorophenyl)porphyrin iron chloride 、 [Cu(pmap)]B(C6F5)4 以 乙腈 为溶剂， 生成 (5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate)FeII 、 [Cu(pmap)Cl]B(C6F5)4
  参考文献：
  名称：

  Intermolecular versus intramolecular electron-/atom- (Cl) transfer in heme-iron and copper pyridylalkylamine complexes

  摘要：

  While outer-sphere electron-transfer reactions come with a firm experimental and theoretical basis, less is known about the redox reactions occurring by atom-transfer. In the present study, relevant reactions occur upon mixing, (F-8)Fe-III(Cl) (F-8 is tetrakis(2,6-difluorophenyl)porphyrinate) with a series of [(L)Cu-I](+) complexes (L are tripodal tetradentate pyridylalkylamine ligands varying in effective chelate ring sizes: TMPA, PMEA, PMAP) to form (F-8)Fe-II and [(L)Cu-II(Cl)](+). The electron-/atom- (Cl-center dot) transfer process is characterized by electrochemical measurements as well as UV-Vis, H-1 NMR, and EPR spectroscopies. Stopped-flow UV-Vis spectroscopy in THF indicate the following relative rates (k(obs)) [Cu-I(pmea)](+) > [Cu-I(pmap)](+) > [Cu-I(tmpa)(thf)](+). However, the redox potentials as related to Delta G degrees for the reaction, [E-1/2(oxidant) - E-1/2(reductant)], predict the trend [Cu-I(tmpa)(CH3CN)](+) > [Cu-I(pmea)](+) > [Cu-I(pmap)](+). A detailed description of Cu-I-to-Cu-II structural changes is provided and these likely influence the observed [(L)Cu-I](+)/(F-8)Fe-III(Cl) reaction rates. Analogous chemistry is described for a heme-copper system utilizing a heterobinucleating ligand (L-6), which is comprised of a TMPA like moiety tethered at the 6-position of one of the pyridyl donors to a F-8-like heme. Kinetic/mechanistic insights were obtained from transient absorption spectroscopic monitoring in CH3CN following photoejection of carbon monoxide from [(L-6)Fe-II(CO) center dot center dot center dot Cu-II(Cl)]. (C) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2007.08.016
• 作为产物：
  描述：

  bis(2-(2-pyridyl)ethyl)(2-pyridylmethyl)amine 、 tetrakis(acetonitrile)copper(I) tetrakis(pentafluorophenyl)borate 以 乙醚 为溶剂， 以74%的产率得到[Cu(pmap)]B(C6F5)4
  参考文献：
  名称：

  铜（I）吡啶基烷基胺化合物中的一氧化碳配位和可逆光解离。

  摘要：

  随着五元螯合环（如1R）到六元螯合环（如2R）的系统合成扩展，CO加合物的稳定性降低，即1H-CO​​> 2 pmea-CO> 2 pmap-CO。3bqpa的CO结合特性没有遵循其他化合物的趋势，这可能是由于其较大的配体骨架。通过固相和溶液状态分析，我们得出结论，溶液中的光不稳定羰基物质具有三齿配位模式，与三脚架配体的一个悬臂形成与铜离子的严格五元螯合环。一氧化碳可在配位（CH3CN）和弱配位（THF）溶剂中从配合物1Me2N-CO，1MeO-CO，1H-CO​​和3bqpa-CO光解离，但不能从2 pmea-CO和2 pmap-CO中解离。

  DOI：

  10.1021/ic701903h