2,5-Difluor-3,6-di-anilino-benzochinon-(1,4) | 1425-96-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,5-Difluor-3,6-di-anilino-benzochinon-(1,4)
• 英文别名: 2,5-Dianilino-3,6-difluorocyclohexa-2,5-diene-1,4-dione
• CAS: 1425-96-3
• 化学式: C₁₈H₁₂F₂N₂O₂
• 分子量: 326.302
• InChiKey: PMSHLOQNXRXAGK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  58.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  、 2,5-Difluor-3,6-di-anilino-benzochinon-(1,4) 、 sodium hexamethyldisilazane 、 三(2-吡啶基甲基)胺 以 四氢呋喃 为溶剂， 反应 12.17h， 以77%的产率得到
  参考文献：
  名称：

  Electronic Effects of Ligand Substitution on Spin Crossover in a Series of Diiminoquinonoid-Bridged Fe^II₂ Complexes

  摘要：

  A series of four isostructural Fe-2(II) complexes, [(TPyA)(2)Fe-2(XL)](2)(+) (TPyA = tris(2-pyridylmethyl)amine; XL2- = doubly deprotonated form of 3,6-disubstituted-2,5-dianilino-1,4-benzoquinone; X = H, Br, Cl, and F), were synthesized to enable a systematic study of electronic effects on spin crossover behavior. Comparison of X-ray diffraction data for these complexes reveals the sole presence of high-spin Fe-II at 225 K and mixtures of high-spin and low-spin Fe-II at 100 K, which is indicative of incomplete spin crossover. In addition, crystal packing diagrams show that these complexes are well-isolated from one another in the solid state, owing primarily to the presence of bulky tetra(aryl)borate counteranions, such that spin crossover is likely not significantly affected by intermolecular interactions. Variable-temperature dc magnetic susceptibility data confirm the structural observations and reveal that 54(1), 56(1), 62(1), and 84(1)% of Fe-II centers remain high-spin even below 65 K. Moreover, fits to magnetic data provide crossover temperatures of T-1/2 = 160(1), 124(1), 121(1), and 110(1) K for X = H, Br, Cl, and F, respectively, along with enthalpies of Delta H = 11.4(3), 8.5(3), 8.3(3), and 7.5(2) kJ/mol, respectively. These parameters decrease with increasing electronegativity of X and thus increasing electron-withdrawing character of L-X(2-), suggesting that the observed trends originate primarily from inductive effects of X. Moreover, when plotted as a function of the Pauling electronegativity of X, both T-1/2 and Delta H undergo a linear decrease. Further analyses of the low-temperature magnetic data and variable-temperature Mossbauer spectroscopy suggest that the incomplete spin crossover behavior in [(TPyA)(2)Fe-2(XL)](2+) is best described as a transition from purely [Fe-HS-Fe-HS] (HS = high-spin) complexes at high temperature to a mixture of [Fe-HS-Fe-HS] and [Fe-HS-Fe-LS] (LS = low-spin) complexes at low temperature, with the number of [Fe-HS-Fe-HS] species increasing with decreasing electron-withdrawing character of L-X(2-).

  DOI：

  10.1021/ic5025586
• 作为产物：
  描述：

  四氟对苯醌 、 苯胺 在 sodium acetate 、 溶剂黄146 作用下， 以 乙醇 、 水 为溶剂， 反应 5.0h， 以88%的产率得到2,5-Difluor-3,6-di-anilino-benzochinon-(1,4)
  参考文献：
  名称：

  Electronic Effects of Ligand Substitution on Spin Crossover in a Series of Diiminoquinonoid-Bridged Fe^II₂ Complexes

  摘要：

  A series of four isostructural Fe-2(II) complexes, [(TPyA)(2)Fe-2(XL)](2)(+) (TPyA = tris(2-pyridylmethyl)amine; XL2- = doubly deprotonated form of 3,6-disubstituted-2,5-dianilino-1,4-benzoquinone; X = H, Br, Cl, and F), were synthesized to enable a systematic study of electronic effects on spin crossover behavior. Comparison of X-ray diffraction data for these complexes reveals the sole presence of high-spin Fe-II at 225 K and mixtures of high-spin and low-spin Fe-II at 100 K, which is indicative of incomplete spin crossover. In addition, crystal packing diagrams show that these complexes are well-isolated from one another in the solid state, owing primarily to the presence of bulky tetra(aryl)borate counteranions, such that spin crossover is likely not significantly affected by intermolecular interactions. Variable-temperature dc magnetic susceptibility data confirm the structural observations and reveal that 54(1), 56(1), 62(1), and 84(1)% of Fe-II centers remain high-spin even below 65 K. Moreover, fits to magnetic data provide crossover temperatures of T-1/2 = 160(1), 124(1), 121(1), and 110(1) K for X = H, Br, Cl, and F, respectively, along with enthalpies of Delta H = 11.4(3), 8.5(3), 8.3(3), and 7.5(2) kJ/mol, respectively. These parameters decrease with increasing electronegativity of X and thus increasing electron-withdrawing character of L-X(2-), suggesting that the observed trends originate primarily from inductive effects of X. Moreover, when plotted as a function of the Pauling electronegativity of X, both T-1/2 and Delta H undergo a linear decrease. Further analyses of the low-temperature magnetic data and variable-temperature Mossbauer spectroscopy suggest that the incomplete spin crossover behavior in [(TPyA)(2)Fe-2(XL)](2+) is best described as a transition from purely [Fe-HS-Fe-HS] (HS = high-spin) complexes at high temperature to a mixture of [Fe-HS-Fe-HS] and [Fe-HS-Fe-LS] (LS = low-spin) complexes at low temperature, with the number of [Fe-HS-Fe-HS] species increasing with decreasing electron-withdrawing character of L-X(2-).

  DOI：

  10.1021/ic5025586

文献信息

• Tetra- and tri-fluoro-p-benzoquinone
  作者：E. Nield、J.C. Tatlow

  DOI：10.1016/s0040-4020(01)93328-9

  日期：1960.1