1,2,3,4,5-pentamethyl-1'-ethynylferrocene | 193421-05-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: 1,2,3,4,5-pentamethyl-1'-ethynylferrocene
• 英文别名: 1,2,3,4,5-pentamethyl-1’-ethynyl-ferrocene；5-ethynylcyclopenta-1,3-diene;iron(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene
• CAS: 193421-05-5
• 化学式: C₁₇H₂₀Fe
• 分子量: 280.193
• InChiKey: RRGIBNBWKONSNE-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：

  1,2,3,4,5-pentamethyl-1'-ethynylferrocene 、 三丁基氯化锡 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.0h， 生成 tributylstannyl-1,2,3,4,5-pentamethyl-1'-ethynylferrocene
  参考文献：
  名称：

  光致变色二茂铁共轭二甲基二氢py衍生物的比较研究

  摘要：

  研究了双（二茂铁基乙炔基）苯并二甲基二氢（（1）和其他苯并二甲基二氢py（BzDHP）衍生物的光化学性质和混合价态，以了解1的电子通信中的可逆光开关。1的吸收光谱通过UV / Vis光谱进行表征，并使用时变密度泛函理论（TD-DFT）进行计算，并且表明二茂铁（Fc）部分的d轨道有助于引起占据的价态轨道对于光致变色行为。1个在THF中表现出可逆的光异构化；然而，在二氯甲烷中未观察到光致变色行为。氧化还原电势分析表明，二氯甲烷中的混合价态1比THF中的稳定。这与以下观察结果一致：化学氧化导致二氯甲烷中混合价为1的Fc部分之间存在间隔电荷转移（IVCT）带，而单电子氧化的1中未观察到该带。四氢呋喃。双（五甲基二茂铁基乙炔基）苯并二甲基二氢py（2）即使在THF中也没有表现出光致变色行为。的混合价态2是更不稳定比的1在二氯甲烷中，并观察到没有明显的IVCT带单电子氧化2在二氯甲烷中。Fc和五甲基二茂铁（Me

  DOI：

  10.1002/chem.201303456
• 作为产物：
  描述：

  1,2,3,4,5-pentamethyl-1'-cis-chlorovinylferrocene 以 neat (no solvent) 为溶剂， 生成 1,2,3,4,5-pentamethyl-1'-ethynylferrocene
  参考文献：
  名称：

  功能化的五甲基二茂铁：合成，结构和电化学

  摘要：

  与普遍存在的Cp配体相比，Cp *配体的有利性质-增强的电子给体，空间位阻和增加的溶解度-在有机金属化学中得到了越来越多的应用。据报道，系统评估了合成途径广泛的五甲基二茂铁化合物的功能，这些化合物包括羧基，羰基，氨基甲基，乙烯基，乙炔基，富烯基，环戊二烯基甲基等。将这种官能化的五甲基二茂铁Fc * / 2 -R的光谱，结构和电化学性质与未甲基化的二茂铁Fc-R的光谱，结构和电化学性质进行比较。这些不对称二茂铁Fc * / 2中Cp *配体的电子影响-R已通过循环伏安法测量进行了研究，与未甲基化的二茂铁茂铁Fc-R直接比较，证明了-0.276 V的氧化电势降低。

  DOI：

  10.1016/s0022-328x(97)00133-2

文献信息

• Synthesis, Redox Activity of Rigid Ferrocenyl Dendrimers, and Isolation of Robust Ferricinium and Class-II Mixed-Valence Dendrimers
  作者：Abdou K. Diallo、Jaime Ruiz、Didier Astruc

  DOI：10.1002/chem.201300560

  日期：2013.7.1

  and 1,2,3,4,5‐pentamethyl‐ferrocenylethynyl redox groups, thus leading to the construction of a dendrimer (7 c) that contains both types of differently substituted ferrocenyl groups with two well‐separated reversible CV waves. Upon selective oxidation, this mixed dendrimer (7 c) leads to a class‐II mixed‐valence dendrimer, 7 c[PF6]3, as shown by Mössbauer spectroscopy, whereas oxidation of the related

  乙炔基二茂铁与三卤代芳烃的偶联反应不会产生可溶的乙炔基二茂铁基芳烃，以形成合适的刚性二茂铁基乙炔基以芳烃为中心的树枝状大分子的基础，这解释了以前关于刚性二茂铁基树枝状大分子的报道。然而，据报道，刚性的二茂铁基封端的树枝状大分子是通过Sonogashira和Negishi反应与1,2,3,4,5-五甲基-1'-乙炔基二茂铁（1 a）由1,3,5-三溴和三碘苯合成的。1→2连接。用化合物1，可溶性树枝状聚合物（的结构10中的含有12 ethynylpentamethylferrocenyl末端）中的溶液来实现。刚性树枝状聚合物10 a显示了一个单一的可逆循环伏安（CV）波（带有吸附），它不利于跳变的异质电子转移机制，该机制被假定为包含柔性系链的氧化还原终止的树枝状大分子。这些Sonogashira反应的选择性允许合成同时含有乙炔基二茂铁基和1,2,3,4,5-五甲基-二茂铁基乙炔基氧化还原基团的芳烃核树枝状分子（2
• Visible-Light Generation of the Naked 12-Electron Fragment C₅H₅Fe⁺: Alkyne-to-Vinylidene Isomerization and Synthesis of Polynuclear Iron Vinylidene and Alkynyl Complexes Including Hexairon Stars
  作者：Yanlan Wang、Abdou K. Diallo、Cátia Ornelas、Jaime Ruiz、Didier Astruc

  DOI：10.1021/ic201206e

  日期：2012.1.2

  compact fluorescent light bulb in the presence of terminal alkynes and dppe yielded the vinylidene complexes [FeCp(═C═CHR)(dppe)][PF6] that were deprotonated by t-BuOK to yield the alkynyl complexes [FeCp(-C≡CR)(dppe)]. The reaction has been extended to the synthesis of bis-, tris, tetra-, and hexanuclear iron complexes including three alkynes of the ferrocenyl family.

  的[FeCp（η可见光光解6 -C 6 H ^ 5 CH 3）] [PF 6 ]使用简单的100-W灯泡或在末端炔烃和DPPE的存在下，紧凑型荧光灯灯泡，得到偏二配合物[FeCp通过t -BuOK使（proC═CHR）（DPPE）] [PF 6 ]质子化，生成炔基配合物[FeCp（-C≡CR）（DPPE）]。该反应已扩展到合成双核，三核，四核和六核铁配合物，其中包括三茂铁基族的三个炔烃。
• 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.