[Cu(fla)(idpaH)]ClO4 | 277314-01-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 2-芳基苯并呋喃类黄酮
• 英文名称: [Cu(fla)(idpaH)]ClO4
• CAS: 277314-01-9
• 化学式: C₂₅H₃₄CuN₃O₃*ClO₄
• 分子量: 587.56
• InChiKey: ZPPDFVJREWZZED-UHFFFAOYSA-L

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：

  [Cu(fla)(idpaH)]ClO4 、 氧气 以 N,N-二甲基甲酰胺 为溶剂， 以62%的产率得到[Cu(idpaH)(o-bs)]ClO4
  参考文献：
  名称：

  Copper-mediated oxygenation of flavonolate in the presence of a tridentate N-ligand. Synthesis and crystal structures of [Cu(fla)(idpaH)]ClO4 and [Cu(idpaH)(O-bs)]ClO4, [fla=flavonolate, idpaH=3,3′-iminobis(N,N-dimethylpropylamine), O-bs=O-benzoylsalicylate]

  摘要：

  The complexes [Cu(fla)(idpaH)] ClO4 (4) and [Cu(idpaH)(O-bs)] ClO4 (5) (fla = flavonolate, idpaH = 3,3'-iminobis(N, N-dimethylpropylamine), O-bs = O-benzoylsalicylate) have been synthesised and characterised. Complex 5 can be obtained also by the oxygenation of 4 and concomitant CO release. The structures of the compounds have been determined by X-ray diffraction. Complex 4 exhibits distorted trigonal-bipyramidal geometry around the copper(II) ion while complex 5 is distorted square-pyramidal. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(00)00071-2
• 作为产物：
  描述：

  copper(II) perchlorate hexahydrate 、 3-羟基黄酮 、 3,3′-亚氨基双(N,N-二甲基丙胺) 在 piperidine 作用下， 以 甲醇 为溶剂， 以90%的产率得到[Cu(fla)(idpaH)]ClO4
  参考文献：
  名称：

  Copper-mediated oxygenation of flavonolate in the presence of a tridentate N-ligand. Synthesis and crystal structures of [Cu(fla)(idpaH)]ClO4 and [Cu(idpaH)(O-bs)]ClO4, [fla=flavonolate, idpaH=3,3′-iminobis(N,N-dimethylpropylamine), O-bs=O-benzoylsalicylate]

  摘要：

  The complexes [Cu(fla)(idpaH)] ClO4 (4) and [Cu(idpaH)(O-bs)] ClO4 (5) (fla = flavonolate, idpaH = 3,3'-iminobis(N, N-dimethylpropylamine), O-bs = O-benzoylsalicylate) have been synthesised and characterised. Complex 5 can be obtained also by the oxygenation of 4 and concomitant CO release. The structures of the compounds have been determined by X-ray diffraction. Complex 4 exhibits distorted trigonal-bipyramidal geometry around the copper(II) ion while complex 5 is distorted square-pyramidal. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(00)00071-2

文献信息

• Carboxylate-enhanced reactivity in the oxygenation of copper flavonolate complexes
  作者：Éva Balogh-Hergovich、József Kaizer、Gábor Speier

  DOI：10.1016/s1381-1169(03)00456-4

  日期：2003.10

  The oxygenolytic cleavage of flavonolate coordinated to copper(II) with the auxiliary ligand 3,3'-iminobis(N,N-dimethyl-propylamine), [Cu-II(fla)(idpa)]ClO4, is enhanced by the addition of acetate and benzoate. Monodentate coordination of the flavonolate forced by the carboxylate ligands is believed to be the reason for the higher reaction rates. (C) 2003 Elsevier B.V. All rights reserved.
• Kinetics and mechanism of the stoichiometric oxygenation of [CuII(fla)(idpa)]ClO4 [fla=flavonolate, idpa=3,3′-imino-bis(N,N-dimethylpropylamine)] and the [CuII(fla)(idpa)]ClO4-catalysed oxygenation of flavonol
  作者：László Barhács、József Kaizer、József Pap、Gábor Speier

  DOI：10.1016/s0020-1693(01)00469-8

  日期：2001.8

  Oxygenation of [Cu-II(fla)(idpa)]ClO4 (fla = flavonolate; idpa = 3,3'-iminobis(N,N-dimethylpropylamine)) in dimethylformamide gives [Cu-II(idpa)(O-bs)]ClO4 (O-bs = O-benzoylsalicylate) and CO. The oxygenolysis of [Cu-II(fla)(idpa)]ClO4 in DMF was followed by electronic spectroscopy and the rate law - d[Cu-II(fla)(idpa)}ClO4]/dt = k(obs)[Cu-II(fla)(idpa)}ClO4][O-2] was obtained. The rate constant, activation enthalpy and entropy at 373 K are k(obs) = 6.13 +/- 0.16 x 10(-3) M-1 s(-1), DeltaH(double dagger) = 64 +/- 5 kJ mol(-1), DeltaS(double dagger) = -120 +/- 13 J mol(-1) K-1, respectively. The reaction fits a Hammett linear free energy relationship and a higher electron density on copper gives faster oxygenation rates. The complex [Cu-II(fla)(idpa)]ClO4 has also been found to be a selective catalyst for the oxygenation of flavonol to the corresponding O-benzoylsalicylic acid and CO. The kinetics of the oxygenolysis in DMF was followed by electronic spectroscopy and the following rate law was obtained: -d[flaH]/dt = k(obs)[Cu-II(fla)(idpa)}ClO4][O-2]. The rate constant, activation enthalpy and entropy at 403 K are k(obs) = 4.22 +/- 0.15 x 10(-2) M-1 s(-1), DeltaH(double dagger) = 71 +/- 6 kJ mol(-1), DeltaS double dagger = -97 +/- 15 J mol(-1) K-1, respectively. (C) 2001 Elsevier Science B.V. All rights reserved.