3,5-diferrocenylaniline | 197068-34-1

• 分子结构分类: 有机化合物 - 碳氢化合物
• 英文名称: 3,5-diferrocenylaniline
• 英文别名: cyclopenta-1,3-diene;3,5-di(cyclopenta-2,4-dien-1-yl)aniline;iron(2+)
• CAS: 197068-34-1
• 化学式: C₂₆H₂₃Fe₂N
• 分子量: 461.169
• InChiKey: BCBFUGRPDREDTG-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：

  3,5-diferrocenylaniline 以 乙腈 为溶剂， 生成
  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：

  3,5-diferrocenylnitrobenzene 、 肼 在 Pd/C 作用下， 以 乙醇 为溶剂， 以96%的产率得到3,5-diferrocenylaniline
  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

文献信息

• Photon-, Electron-, and Proton-Induced Isomerization Behavior of Ferrocenylazobenzenes
  作者：Aiko Sakamoto、Akira Hirooka、Kosuke Namiki、Masato Kurihara、Masaki Murata、Manabu Sugimoto、Hiroshi Nishihara

  DOI：10.1021/ic051184r

  日期：2005.10.1

  several derivatives of 1 were synthesized, and their photoisomerization behaviors were examined. The molecular structures of 1 and its derivatives, 2-chloro-5-ferrocenylazobenzene (5) and 3-ferrocenyl-4'-hydroxylazobenzene (11), were determined by X-ray diffraction analysis. 3-Ferrocenyl compound 1 undergoes reversible trans-to-cis isomerization with a single green light source and the Fe(III)/Fe(II)

  分别合成了3-，4-和2-二茂铁基偶氮苯，1、2和3，以及1的几种衍生物，并研究了它们的光异构化行为。通过X射线衍射分析确定了1及其衍生物2-氯-5-二茂铁基偶氮苯（5）和3-二茂铁基-4'-羟基叠氮苯（11）的分子结构。3-二茂铁基化合物1在单个绿色光源和Fe（III）/ Fe（II）氧化还原变化下经历可逆的反式-顺式异构化。4-和2-二茂铁基化合物2和3除紫外线外还响应绿光，激发pi-pi *跃迁，但在光平稳态（PSS）中的顺式摩尔比低于1。在2和3中对绿光的响应是由MLCT波段（从Fe d轨道到偶氮pi *轨道）激发引起的，而MLCT波段的特性是，由随时间变化的密度泛函理论计算得出的结果介于1和2之间。2的氧化形式容易进行顺式-反式热异构化。1和2都经过容易的质子化，并显示出质子催化的顺-反异构化。1的衍生物中，2-氯-5-二茂铁基偶氮苯（5）在绿光照射的PSS中表现出最高的顺式摩尔比（47％）。