[(Cu(I)(N,N-bis(2-[2-(N'N'-4-dimethylamino)pyridyl]ethyl)methylamine)][B(C6F5)4] | 494191-00-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [(Cu(I)(N,N-bis(2-[2-(N'N'-4-dimethylamino)pyridyl]ethyl)methylamine)][B(C6F5)4]
• 英文别名: [(Cu(I)(MePY2)(Me2N))][B(C6F5)4]；copper(1+);2-[2-[2-[4-(dimethylamino)pyridin-2-yl]ethyl-methylamino]ethyl]-N,N-dimethylpyridin-4-amine;tetrakis(2,3,4,5,6-pentafluorophenyl)boranuide
• CAS: 494191-00-3
• 化学式: C₁₉H₂₉CuN₅*C₂₄BF₂₀
• 分子量: 1070.06
• InChiKey: HSCYPVBVMXSRFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.17
• 重原子数：
  70
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  26

反应信息

• 作为反应物：
  描述：

  [(Cu(I)(N,N-bis(2-[2-(N'N'-4-dimethylamino)pyridyl]ethyl)methylamine)][B(C6F5)4] 、 氧气 以 二氯甲烷 为溶剂， 生成 [(Me2N-MePY2)2Cu2(μ-η(2):η(2)-O2)][B(C6F5)4]2
  参考文献：
  名称：

  通过配体电子学中的改变调节铜-双氧反应性和外源性底物氧化

  摘要：

  铜 (I)-双氧加合物在生物和工业过程中很重要。我们第一次探索了配体电子学、CuI-O2 加合物形成和外源底物反应性之间的关系。制备了铜 (I) 配合物 [CuI(R-MePY2)]+ (1R, 其中 R = Cl, H, MeO, Me2N)；其中R-MePY2是4-吡啶基取代的双[2-(2-吡啶基)乙基]甲胺螯合物。1R 的氧化还原电位（范围从 1Cl 的 E1/2 = -270 mV 到 1MeN 的 -440 mV vs FeCp2/FeCp2+）和 1R 的 CO 加合物的 nuCO（范围从 1Cl-CO 的 2093 cm-1 到 2075 cm-1 for 1Me2N-CO) 显示适度但预期的系统变化。双氧很容易与 1H、1MeO 和 1Me2N 反应，形成侧面的过氧-CuII2 复合物 [{CuII(R-MePY2)}2(O2)]2+ (2R，也包含一些双-mu-氧-CuIII2

  DOI：

  10.1021/ja028779v

文献信息

• A μ-η2:η2-Disulfide Dicopper(II) Complex from Reaction of S8 with a Copper(I) Precursor: Reactivity of the Bound Disulfur Moiety
  作者：Matthew E. Helton、Debabrata Maiti、Lev N. Zakharov、Arnold L. Rheingold、John A. Porco、Kenneth D. Karlin

  DOI：10.1002/anie.200503216

  日期：2006.2.6
• Substrate Oxidation by Copper−Dioxygen Adducts:  Mechanistic Considerations
  作者：Jason Shearer、Christiana Xin Zhang、Lev N. Zakharov、Arnold L. Rheingold、Kenneth D. Karlin

  DOI：10.1021/ja045191a

  日期：2005.4.1

  A series of copper-dioxygen adducts [Cu-II(MePY2)(R)}(2)(O-2)](B(C6F5)(4))(2) (1(R)), systematically varying in their electronic properties via ligand pyridyl donor substituents (R = H, MeO, and Me2N), oxidize a variety of substrates with varying C-H or O-H bond dissociation enthalpies. Detailed mechanistic studies have been carried out, including investigation of 1(R) thermodynamic redox properties, 1(R) tetrahydrofuran (THF) and N,N'-dimethylaniline (DMA) oxidation kinetics (including analyses of substrate dicopper binding equilibria), and application of mechanistic probes (N-cyclopropyl-N-methylaniline (CMA) and (p-methoxyphenyl)-2,2-dimethylpropanol (MDP)), which can distinguish if proton-coupled electron-transfer (PCET) processes proceed through concerted electron-transfer proton-transfer (ETPT) or consecutive electron-transfer proton-transfer (ET/PT) pathways. The results are consistent with those of previous complementary studies; at low thermodynamic driving force for substrate oxidation, an ET/PT is operable, but once ET (i.e., substrate one-electron oxidation) becomes prohibitively uphill, the ETPT pathway occurs. Possible differences in coordination structures about 1(Me2N)/1(MeO) compared to those of 1(H) are also used to rationalize some of the observations.