H3felddien | 1350744-38-5

• 分子结构分类: 有机化合物
• 英文名称: H3felddien
• 英文别名: 2,4,6-Tris[2-[2-(dimethylamino)ethyl-methylamino]ethyliminomethyl]benzene-1,3,5-triol
• CAS: 1350744-38-5
• 化学式: C₃₀H₅₇N₉O₃
• 分子量: 591.841
• InChiKey: OOAIUHCETDRDBQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  42
• 可旋转键数：
  21
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  117
• 氢给体数：
  3
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  nickel(II) tetrafluoroborate hexahydrate 、 H3felddien 在 NEt₃ 作用下， 以 甲醇 为溶剂， 以59%的产率得到[(felddien)Ni3](BF4)3
  参考文献：
  名称：

  Synthesis and characterization of trinuclear square-planar NiII3 and CuII3 complexes of an extended phloroglucinol ligand: Experimental evidence for the relative contributions of benzene-like and radialene-like resonance structures

  摘要：

  The synthesis and characterization of the extended phloroglucinol ligand H(3)felddien, its trinuclear Ni-II complex [(felddien)Ni-3](BF4)(3) and its trinuclear Cu-II complex [(felddien)Cu-3](ClO4)(3) is presented. Detailed NMR studies provide strong evidence that the ligand H(3)felddien has to be described as the N-protonated tautomer and not as the O-protonated tautomer, with strong contribution of a radialene-like keto-enamine resonance structure resulting in a C-s and a C-3h isomer. The trinucleating tris(tetradentate) ligand provides three donor sets comprised of a phenolate, an imine, and two tertiary amine donors. This donor set enables the synthesis of the diamagnetic square-planar coordinated Ni-II complex [(felddien)Ni-3](BF4)(3) which provides the opportunity to perform detailed NMR spectroscopic characterizations for the evaluation of the electronic structure of the central phloroglucinol unit. In conjunction with a single-crystal Xray diffraction and a UV-vis absorption spectroscopic analysis, these data indicate that in the coordinated form, the benzene-like phenolate-imine and the radialene-like keto-enamine resonance structures have contributions to the overall resonance hybrid. The weakening of the central pi system as a consequence of the contribution of the keto-enamine resonance structure explains the relative small ferromagnetic interactions in the trinuclear Cu-II complex [(felddien)Cu-3](ClO4)(3). This detailed analysis identifies the strong resonance with unsaturated groups in 2,4,6 position of phloroglucinol as the main source for the low ferromagnetic couplings by the spin-polarization mechanism in all our extended phloroglucinol ligands. A replacement of the unsaturated imine functions by saturated amine functions may be a synthetic opportunity to enhance the ferromagnetic interactions by the spin-polarization mechanism in this ligand system. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2011.02.029
• 作为产物：
  描述：

  N-(2-氨基乙基)-N,N',N'-三甲基乙烷-1,2-二胺 、 三醛基间苯三酚 以 二氯甲烷 为溶剂， 反应 12.0h， 以78%的产率得到H3felddien
  参考文献：
  名称：

  Synthesis and characterization of trinuclear square-planar NiII3 and CuII3 complexes of an extended phloroglucinol ligand: Experimental evidence for the relative contributions of benzene-like and radialene-like resonance structures

  摘要：

  The synthesis and characterization of the extended phloroglucinol ligand H(3)felddien, its trinuclear Ni-II complex [(felddien)Ni-3](BF4)(3) and its trinuclear Cu-II complex [(felddien)Cu-3](ClO4)(3) is presented. Detailed NMR studies provide strong evidence that the ligand H(3)felddien has to be described as the N-protonated tautomer and not as the O-protonated tautomer, with strong contribution of a radialene-like keto-enamine resonance structure resulting in a C-s and a C-3h isomer. The trinucleating tris(tetradentate) ligand provides three donor sets comprised of a phenolate, an imine, and two tertiary amine donors. This donor set enables the synthesis of the diamagnetic square-planar coordinated Ni-II complex [(felddien)Ni-3](BF4)(3) which provides the opportunity to perform detailed NMR spectroscopic characterizations for the evaluation of the electronic structure of the central phloroglucinol unit. In conjunction with a single-crystal Xray diffraction and a UV-vis absorption spectroscopic analysis, these data indicate that in the coordinated form, the benzene-like phenolate-imine and the radialene-like keto-enamine resonance structures have contributions to the overall resonance hybrid. The weakening of the central pi system as a consequence of the contribution of the keto-enamine resonance structure explains the relative small ferromagnetic interactions in the trinuclear Cu-II complex [(felddien)Cu-3](ClO4)(3). This detailed analysis identifies the strong resonance with unsaturated groups in 2,4,6 position of phloroglucinol as the main source for the low ferromagnetic couplings by the spin-polarization mechanism in all our extended phloroglucinol ligands. A replacement of the unsaturated imine functions by saturated amine functions may be a synthetic opportunity to enhance the ferromagnetic interactions by the spin-polarization mechanism in this ligand system. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2011.02.029