flavonolatobis(triphenylphosphine)copper(I) | 128000-73-7

• 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: flavonolatobis(triphenylphosphine)copper(I)
• 英文别名: flavonatobis(triphenylphosphine)copper(I)；copper(1+);4-oxo-2-phenylchromen-3-olate;triphenylphosphane
• CAS: 128000-73-7
• 化学式: C₅₁H₃₉CuO₃P₂
• 分子量: 825.362
• InChiKey: BDDAVHIKOWLWII-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.42
• 重原子数：
  57
• 可旋转键数：
  7
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  49.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  flavonolatobis(triphenylphosphine)copper(I) 、 氧气 以 N,N-二甲基甲酰胺 为溶剂， 生成 Cu(PPh3)2(O-benzoylsalicylate)2
  参考文献：
  名称：

  Quercetin 2,3-Dioxygenase Mimicking Ring Cleavage of the Flavonolate Ligand Assisted by Copper. Synthesis and Characterization of Copper(I) Complexes [Cu(PPh₃)₂(fla)] (fla = Flavonolate) and [Cu(PPh₃)₂(O-bs)] (O-bs = O-Benzoylsalicylate)

  摘要：

  Cu(PPh3)(2)(fla) has been prepared by reacting copper(I) chloride with sodium flavonolate in tetrahydrofuran solution. Crystallographic characterization of the complex (orthorhombic, P2(1)2(1)2(1), a = 9.588(1) Angstrom, b = 17.364(3) Angstrom, c = 24.378(3) Angstrom, V = 4058.6(10) Angstrom(3), Z = 4, R = 0.049) has shown that the coordination geometry of the molecule is tetrahedral. Oxygenation of Cu(PPh3)(2)(fla) in a methylene chloride solution at ambient conditions gives the O-benzoylsalicylato copper complex Cu(PPh3)(2)(O-bs) and carbon monoxide. Labeling experiments with an O-18(2)-O-16(2) mixture (1:4) evidenced the incorporation of both O-18 atoms of O-18(2) into the O-bs ligand. IR and MS studies of labeled O-bs confirmed the incorporation of O-18(2) while the released CO remained unlabeled. Crystallographic characterization of Cu(PPh3)(2)(O-bs) on crystals obtained as the acetone solvate (triclinic, P (1) over bar, a = 13.154(1) Angstrom, b = 17.991(1) Angstrom, c = 20.495(1) Angstrom, alpha = 80.01(1)degrees, beta = 88.02(1)degrees, gamma = 71.83(1)degrees, V = 4537.5(5) Angstrom(3), Z = 4, R = 0.0403) shows that the molecule has a distorted tetrahedral structure. The oxygenolysis was followed by spectrophotometry, and the rate constants were determined according to the rate law -d[Cu(PPh3)(2)(fla)]/dt = k(2)[Cu(PPh3)(2)(fla)][O-2]. The rate constant, activation enthalpy, and entropy at 363.16 K are as follows: k(2)/M-1 s(-1) = 4.16 +/- 0.48, Delta H double dagger/kJ mol(-1) = 102 +/- 7, Delta S double dagger/J mol(-1) K-1 = -13.0 +/- 21. The reaction fits a Hammett linear free energy relationship for 4'-substituted flavonolates, and an increase of the electron density on copper makes the oxygenation reaction faster.

  DOI：

  10.1021/ic990175d
• 作为产物：
  描述：

  3-羟基黄酮 、 三苯基膦 、 copper(l) chloride 以 四氢呋喃 为溶剂， 生成 flavonolatobis(triphenylphosphine)copper(I)
  参考文献：
  名称：

  黄酮双（三苯基膦）铜（I）中的螯合黄酮醇配位（I）

  摘要：

  X-射线晶体结构测定表明，3-羟基黄酮通过其3-羟基和4-羰基与两个三苯基膦与铜（I）配位，形成在黄酮酸酯配体上具有高电子离域的扭曲的四面体。。

  DOI：

  10.1039/c39900000512