ethynylferrocene | 12215-45-1

• 分子结构分类: 有机化合物 - 碳氢化合物
• 英文名称: ethynylferrocene
• 英文别名: MeCpFe(C5H4C2H)；iron(II) 1-ethynylcyclopenta-2,4-dien-1-ide 1-methylcyclopenta-2,4-dien-1-ide；2-ethynylcyclopenta-1,3-diene;iron(2+);2-methylcyclopenta-1,3-diene
• CAS: 12215-45-1
• 化学式: C₁₃H₁₂Fe
• 分子量: 224.085
• InChiKey: WSJOMDXJSLEWLJ-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：

  六溴苯 、 ethynylferrocene 以60%的产率得到hexakis(1-methyl-1'-ferrocenylethynyl)benzene
  参考文献：
  名称：

  刚性分子平台周围的氧化还原基团如何表现？六（二茂铁基乙炔基）苯及其“静电”氧化还原化学

  摘要：

  Negishi偶联通过乙炔基二茂铁和C 6 Br 6合成了一个新的六（二茂铁基乙炔基）苯族，并且可以可逆地氧化成稳定的六茂铁鎓盐（参见图片，Ar F = [3,5-C 6 H 3（CF 3））2 ]）。它们的循环伏安图显示单个六电子波，三个截然不同的两个电子波或六个六个单电子波的级联，具体取决于电解质的抗衡离子和二茂铁基上的甲基取代基数量。

  DOI：

  10.1002/anie.200900216
• 作为产物：
  描述：

  [(η5-C5H4Me)Fe(η5-C5H4COMe)] 在 LiNiPr₂ 、 PO(Cl)Et₂ 作用下， 生成 ethynylferrocene
  参考文献：
  名称：

  刚性分子平台周围的氧化还原基团如何表现？六（二茂铁基乙炔基）苯及其“静电”氧化还原化学

  摘要：

  Negishi偶联通过乙炔基二茂铁和C 6 Br 6合成了一个新的六（二茂铁基乙炔基）苯族，并且可以可逆地氧化成稳定的六茂铁鎓盐（参见图片，Ar F = [3,5-C 6 H 3（CF 3））2 ]）。它们的循环伏安图显示单个六电子波，三个截然不同的两个电子波或六个六个单电子波的级联，具体取决于电解质的抗衡离子和二茂铁基上的甲基取代基数量。

  DOI：

  10.1002/anie.200900216

文献信息

• Star shaped ferrocenyl truxenes: synthesis, structure and properties
  作者：Rajneesh Misra、Rekha Sharma、Shaikh M. Mobin

  DOI：10.1039/c4dt00210e

  日期：——

  This article reports the design and synthesis of star shaped, C3-symmetric ferrocenyl substituted truxenes by the Pd-catalyzed Sonogashira cross-coupling and cycloaddition reaction. The single photon absorption and electrochemical properties indicate significant electronic interaction between ferrocene and truxene core. The bathochromic shift in the absorption spectra of truxenes 4a–4c and 5a is a function of enhanced conjugation. The incorporation of tetracyanoethylene (TCNE) results in a strong charge transfer band in truxene 5a. The single crystal structure of truxene 4a is presented, which shows interesting supramolecular interactions.

  本文报道了通过钯催化的 Sonogashira 交叉偶联和环加成反应设计和合成星形、C3 对称二茂铁取代的三并烯。单光子吸收和电化学特性表明二茂铁和三并烯核心之间存在显著的电子相互作用。三并烯 4a-4c 和 5a 吸收光谱中的浴色偏移是共轭作用增强的结果。加入四氰基乙烯（TCNE）后，三亚甲苯 5a 中出现了一个强电荷转移带。研究还展示了三并烯 4a 的单晶结构，其中显示了有趣的超分子相互作用。
• Ferrocenyl-Terminated Redox Stars: Synthesis and Electrostatic Effects in Mixed-Valence Stabilization
  作者：Abdou K. Diallo、Christelle Absalon、Jaime Ruiz、Didier Astruc

  DOI：10.1021/ja109380u

  日期：2011.1.26

  A family of rigid ferrocenyl-terminated redox stars has been synthesized-by Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tethers and fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenyl-ethynyl)benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu4PF6 as the supporting electrolyte on a Pt anode in CH2Cl2, whereas three distinct two-electron reversible CV waves are observed using Nn-Bu4BAr4F (Ar-F = 3,5-C6H3-(CF3)(2)). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu4PF6 and three one-electron waves using Nn-Bu4BAr4F. This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between para-ferrocenyl groups in 1,4-bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu4BAr4F as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu4BAr4F, which is attributed to the transoid conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, Delta E-p is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transoid position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon.