[Cu(tmpa)Cl]B(C6F5)4 | 1409942-15-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Cu(tmpa)Cl]B(C6F5)4
• 英文别名: copper;1-pyridin-2-yl-N,N-bis(pyridin-2-ylmethyl)methanamine;tetrakis(2,3,4,5,6-pentafluorophenyl)boranuide;chloride
• CAS: 1409942-15-9
• 化学式: C₁₈H₁₈ClCuN₄*C₂₄BF₂₀
• 分子量: 1068.41
• InChiKey: INVFZCIXHBMGBQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.92
• 重原子数：
  69
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  41.9
• 氢给体数：
  0
• 氢受体数：
  26

反应信息

• 作为产物：
  描述：

  5,10,15,20-(tetra-2,6-difluorophenyl)porphyrin iron chloride 、 [(tris(2-pyridylmethylamine))Cu^I(MeCN)][B(C₆F₅)₄] 以 乙腈 为溶剂， 生成 (5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate)FeII 、 [Cu(tmpa)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