1,4-disferrocenylbenzene | 56712-08-4

• 分子结构分类: 有机化合物 - 碳氢化合物
• 英文名称: 1,4-disferrocenylbenzene
• 英文别名: 1,4-diferrocenylbenzene；1,4-diferrocenebenzene；p-diferrocenylbenzene；cyclopenta-1,3-diene;1-cyclopenta-1,4-dien-1-yl-4-cyclopenta-2,4-dien-1-ylbenzene;iron(2+)
• CAS: 56712-08-4
• 化学式: C₂₆H₂₂Fe₂
• 分子量: 446.155
• InChiKey: GRIXTWJQOMRNTH-UHFFFAOYSA-N

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：

  1,4-disferrocenylbenzene 以 乙腈 为溶剂， 生成 1,4-disferrocenylbenzene(1+)
  参考文献：
  名称：

  Topological Effects on Intramolecular Electron Transfer via Quantum Interference

  摘要：

  The three isomers of diferrocenylbenzenes (ortho, 1o; meta, 1m; para, 1p) as well as 5-substituted derivatives of m-diferroceylbenzene with R = NH2 (2), Cl (3), CH3 (4), CN (5), NO2 (6), and N(CH3)(3)(3+) (7) have been prepared. Crystal structures of 10, 3, and 5 have been solved. In 3 and 5, the cyclopentadienyl rings are nearly parallel to the benzene mean planes with angles ranging from 9.99(5)degrees to 14.74(5)degrees. One ferrocene group is above and the other below the mean molecular plane. For lo, there is an important twist between the benzene and cyclopentadiene rings (68.6(8)degrees and 32.5(8)degrees) for steric reasons. Controlled potential electrolysis yields the mixed-valence ferrocene/ ferrocenium species in comproportionation equilibrium with homovalent species. Intervalence transitions have been observed and corrected from comproportionation. From the intervalence band parameters, metal-metal couplings (V-ab) are calculated using Hush's equation. The values are much higher for 1o (0.025 eV) and 1p (0.043 eV) than for 1m (0.012 eV) and exhibit little or no variation for the substituted m-diferrocenylbenzenes 2-6. These results are rationalized by extended Huckel molecular orbital calculations. The weakness of the interaction in Im can be ultimately traced to a quantum Interference effect, i.e., a cancellation of the contributions of two electron transfer paths. This cancellation occurs because each path implies a mixing of metal orbitals with a different ligand orbital, and the resulting molecular orbitals exhibit different symmetries.

  DOI：

  10.1021/ic970013m
• 作为产物：
  描述：

  溴代二茂铁 、 1,4-二碘苯 在 BuLi 、 ZnCl₂ 、 Pd(PPh₃)4 作用下， 以 四氢呋喃 为溶剂， 以57%的产率得到1,4-disferrocenylbenzene
  参考文献：
  名称：

  Topological Effects on Intramolecular Electron Transfer via Quantum Interference

  摘要：

  The three isomers of diferrocenylbenzenes (ortho, 1o; meta, 1m; para, 1p) as well as 5-substituted derivatives of m-diferroceylbenzene with R = NH2 (2), Cl (3), CH3 (4), CN (5), NO2 (6), and N(CH3)(3)(3+) (7) have been prepared. Crystal structures of 10, 3, and 5 have been solved. In 3 and 5, the cyclopentadienyl rings are nearly parallel to the benzene mean planes with angles ranging from 9.99(5)degrees to 14.74(5)degrees. One ferrocene group is above and the other below the mean molecular plane. For lo, there is an important twist between the benzene and cyclopentadiene rings (68.6(8)degrees and 32.5(8)degrees) for steric reasons. Controlled potential electrolysis yields the mixed-valence ferrocene/ ferrocenium species in comproportionation equilibrium with homovalent species. Intervalence transitions have been observed and corrected from comproportionation. From the intervalence band parameters, metal-metal couplings (V-ab) are calculated using Hush's equation. The values are much higher for 1o (0.025 eV) and 1p (0.043 eV) than for 1m (0.012 eV) and exhibit little or no variation for the substituted m-diferrocenylbenzenes 2-6. These results are rationalized by extended Huckel molecular orbital calculations. The weakness of the interaction in Im can be ultimately traced to a quantum Interference effect, i.e., a cancellation of the contributions of two electron transfer paths. This cancellation occurs because each path implies a mixing of metal orbitals with a different ligand orbital, and the resulting molecular orbitals exhibit different symmetries.

  DOI：

  10.1021/ic970013m
• 作为试剂：
  描述：

  甲醇 在 1,4-disferrocenylbenzene 、 铂 三乙醇胺 作用下， 以 甲醇 为溶剂， 生成 氢气
  参考文献：
  名称：

  Photocatalytic Behavior of Di- and Triferrocenylbenzenes on Reduction of Methyl Viologen and Photochemical Hydrogen Evolution from Methanol under Visible Light

  摘要：

  1,4- 和 1,3-Diferrocenylbenzenes (1a 和 1b)、1,2,4- 和 1,3,5-trifrocenylbenzenes (1c 和 1d)可作为光催化剂，在可见光照射下，从 1-methyl viologen MV2+-triethanolamine-colloidal Pt-catalyst 体系中的甲醇中进行光化学氢演化。1 的光催化活性顺序为 1d>1c>1a>1b 。1 的催化活性与 E1⁄2 值相关。在波长为 λ>440 nm 的区域中，1 起着光催化剂的作用，而在波λ<440 nm 的区域中，1 起着淬灭 MV\underset.+ 生成的作用。在太阳光强度最大的波长区域，1 催化形成的 MV\underset.+ 的量子产率最高（1d：QMV\underset.+=0.028, 波长为 480 nm）。

  DOI：

  10.1246/bcsj.59.3589

文献信息

• Bis(ferrocenyl)mercury as a source of ferrocenyl moiety in Pd-catalyzed reactions of carbon–carbon bond formation
  作者：Irina P Beletskaya、Alexei V Tsvetkov、Gennadij V Latyshev、Victor A Tafeenko、Nikolai V Lukashev

  DOI：10.1016/s0022-328x(01)00979-2

  日期：2001.12

  The application of bis(ferrocenyl)mercury as a source of ferrocenyl group in Pd-catalyzed reactions with aryl halides, acid chlorides and electrophilic alkynes has been demonstrated. The formation of dimethyl-(Z)-2,3-di(ferrocenyl)-2-butenedioate in Pd-catalyzed addition of bis(ferrocenyl)mercury to dimethylacetylenedicarboxylate has been confirmed by X-ray analysis. (C) 2001 Elsevier Science BN. All rights reserved.