Cu(II)tris(pyrid-2-ylmethyl)amine(N3) | 92788-04-0

• 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(II)tris(pyrid-2-ylmethyl)amine(N3)
• 英文别名: [Cu(tris(2-pyridylmethyl)amine)(N3)](1+)；CuN3(tris(2-pyridylmethyl)amine)(1+)
• CAS: 92788-04-0
• 化学式: C₁₈H₁₈CuN₇
• 分子量: 395.934
• InChiKey: CIOMPAYYTQCFQF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.94
• 重原子数：
  26.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  100.61
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  氧气 、 Cu(II)tris(pyrid-2-ylmethyl)amine(N3) 以 丙酮 为溶剂， 生成 [{(TMPA)Cu^II}₂(O2²⁻)]²⁺
  参考文献：
  名称：

  受分子内氢键相互作用调节的（μ-过氧）二铜配合物的热稳定性和吸收光谱行为

  摘要：

  为了阐明氢键对具有反式-μ-1,2-过氧形式的（μ-过氧）二铜配合物稳定性的影响，合成了具有分子内氢键相互作用位点的新型铜配合物，及其光谱性质和热稳定性研究。选定的三足四齿配体是三（2-吡啶基甲基）胺（TPA）衍生物，在 TPA 中吡啶环的 6 位带有新戊酰胺和氨基，{[6-（新戊酰胺）吡啶-2-基]甲基}双(吡啶-2-基甲基)胺(MPPA)和[(6-氨基吡啶-2-基)甲基]双(吡啶-2-基甲基)胺(MAPA)。具有 N3− 的单体 CuII 配合物的单晶 X 射线结构，即 [Cu(mppa)N3]ClO4 (1a)，揭示了 MPPA 的取代基 NH 与轴向叠氮氮原子之间的配位氢键相互作用。位置。MPPA 和 MAPA 的 CuI 配合物在 -78 °C 的丙酮溶液中立即用双氧氧化得到 μ-过氧双核铜（II）配合物 [{Cu(mppa)}2(O2)]2+ (1b) 和[{Cu(mapa)}2(O2)]2+

  DOI：

  10.1002/ejic.200300178
• 作为产物：
  描述：

  三(2-吡啶基甲基)胺 在 高氯酸 、 N,N,N’,N’-四乙基乙二胺 、 N,N,N,N-tetraethylammonium tetrafluoroborate 作用下， 以 aq. buffer 为溶剂， 生成 Cu(II)tris(pyrid-2-ylmethyl)amine(N3)
  参考文献：
  名称：

  Understanding the Fundamentals of Aqueous ATRP and Defining Conditions for Better Control

  摘要：

  Conducting an atom transfer radical polymerization (ATRP) in water provides several intriguing challenges. In order to attain a deeper understanding of the mechanism of aqueous ATRP, with particular attention to the reasons for the potential loss of control, a systematic investigation was carried out with three copper-amine catalysts([(CuL)-L-II](2+), L = PMDETA, TPMA and Me6TREN). The association constants (K-x) of [(CuL)-L-II](2+) and [(CuL)-L-I](+) with X- and OH-, as well as the relative stabilities and redox properties of the complexes, were determined as a function of both [X-] and pH. In addition, rate constants and equilibrium constants of disproportionation for all three [(CuL)-L-I](+) complexes were measured. Finally, ATRP equilibrium constants (K-ATRP) were estimated for all complexes, using 2-hydroxyethyl 2-bromoisobutyrate (HEBiB) as initiator. The primary factors affecting control in aqueous ATRP were identified as catalyst instability at both low and high pH, easy dissociation of deactivator (K-x < 15), very high K-ATRP and fast disproportionation of [(CuL)-L-I](+) Overall, the results obtained in this study provide a set of guidelines for a well-controlled aqueous ATRP. The guidelines were used to conduct several efficient electrochemically mediated aqueous ATRP experiments with oligo(ethylene oxide) methyl ether methacrylate as monomer, HEBiB as initiator and copper complexes with three different ligands. A successful ATRP in a strongly acidic environment (pH 1.5) is reported for the first time, contrary to what was believed until now, indicating that ATRPs can be easily controlled in acidic conditions, while high pH should be avoided.

  DOI：

  10.1021/acs.macromol.5b01454