1,4-bis(ferrocenyl)-1,3-butadiyne | 1273-18-3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1,4-bis(ferrocenyl)-1,3-butadiyne
• 英文别名: 1,4-diferrocenyl butadiyne；1,4-diferrocenyl-1,3-butadiyne
• CAS: 1273-18-3
• 化学式: C₂₄H₁₈Fe₂
• 分子量: 418.101
• InChiKey: NFEUXBBVTYVKHV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,4-bis(ferrocenyl)-1,3-butadiyne 以 1,2-二氯乙烷 为溶剂， 生成 1,4-di(ferrocenyl)butadiyne(1+)
  参考文献：
  名称：

  Long-Range Intramolecular Electronic Communication in Bis(ferrocenylethynyl) Complexes Incorporating Conjugated Heterocyclic Spacers: Synthesis, Crystallography, and Electrochemistry

  摘要：

  A new series of bis(ferrocenylethynyl) complexes, 3-7, and a mono(ferrocenylethynyl) complex, 8, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV-vis spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltamrnetry and spectroelectrochemistry. Although there is a large separation of,similar to 14 angstrom between the two redox centers, Delta E-1/2 values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV-vis-near-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc-C C-C C-Fc (Fc = C5H5FeC5H4) highest occupied molecular orbital.

  DOI：

  10.1021/ic3024887
• 作为产物：
  描述：

  [(ferrocenyl)CC]2Cd 以 四氢呋喃 为溶剂， 以99%的产率得到1,4-bis(ferrocenyl)-1,3-butadiyne
  参考文献：
  名称：

  炔基Ti–M配合物，其中M = Cd和Hg：合成，表征和反应化学

  摘要：

  合成和异核的Ti的特性-型的镉络合物{钛[Ti]（μ-η 1：η 2 -C CR）2 } CDX 2（钛[Ti] =的Ti（η 5 -C 5 H ^ 4森达3）2 ; R =森达3：图3a，X =氯;图3b，X = Br的;图3c，X = I; R = Fc结构：3D，X = Br的; FC =铁（η 5 -C 5 H ^ 4）（η 5 - ç 5 ħ 5）报道，这些化合物是由治疗的钛[Ti（C访问CR）2（1a，R ＝ SiMe 3；1b，R ＝ Fc）与镉盐CdX 2（2a，X ＝ Cl；2b，X ＝ Br；2c，X ＝ I）在乙醚中的比例为1∶1M。例如，将3b溶于四氢呋喃中，与镊子分子1a一起提供了配位聚合物[Cd（μ-Br）2（thf）2 ] n（4）。的治疗3B具有两个当量LIC的CFC（5），得到{[钛]（μ-η 1：η 2 -C CSiMe 3）2} Cd（C CFc）2（

  DOI：

  10.1016/j.jorganchem.2011.03.042
• 作为试剂：
  描述：

  甲氧苯胺 在 1,4-bis(ferrocenyl)-1,3-butadiyne 、 copper(l) chloride 作用下， 生成 4,4''-二甲氧基氧化偶氮苯
  参考文献：
  名称：

  Synthesis of 2,5-diferrocenyl five-membered heterocyclic compounds and their electrochemistry

  摘要：

  A series of 2,5-diferrocenyl substituted five-membered heterocyclic compounds, 2,5-diferrocenyl-1-phenylpyrrole (1), 2,5-diferrocenyl-1-(4-fluorophenyl)-pyrrole (2), 2,5-diferrocenyl-1-(4-ethoxyphenyl)-pyrrole (3), 2,5-diferrocenyl-1-(4-ethylphenyl)-pyrrole (4), 2,5-diferrocenylthiophene (5), and 2,5-diferrocenylfuran (6), were synthesized using one-pot cycloaddition of ferrocenyl alkyne and characterized by elemental analysis, FT-IR, MS, and NMR. The molecular structures of 1, 2, 5, and 6 were determined using single-crystal X-ray diffraction. Electronic communication between two ferrocenyl units of 1-6 was investigated using cyclic voltammetry. These compounds have two well-resolved electrochemically reversible one-electron-transfer processes using [NBu4][PF6] as the supporting electrolyte. The electrochemical studies reveal that electronic communication between two ferrocenyl units depend on the heteroatoms.

  DOI：

  10.1080/00958972.2013.841902

文献信息

• How Do Redox Groups Behave around a Rigid Molecular Platform? Hexa(ferrocenylethynyl)benzenes and Their “Electrostatic” Redox Chemistry
  作者：Abdou K. Diallo、Jean-Claude Daran、François Varret、Jaime Ruiz、Didier Astruc

  DOI：10.1002/anie.200900216

  日期：2009.4.14

  A new family of hexakis(ferrocenylethynyl)benzenes was synthesized by Negishi coupling from ethynylferrocenes and C6Br6 and can be reversibly oxidized to stable hexaferrocenium salts (see picture, ArF=[3,5‐C6H3(CF3)2]). Their cyclic voltammograms show a single six‐electron wave, three distinct two‐electron waves, or a cascade of six single‐electron waves, depending on the electrolyte counterion and

  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。
• Regioselectivity in the Sonogashira coupling of 4,6-dichloro-2-pyrone
  作者：Ian J. S. Fairlamb、Ciara T. O'Brien、Zhenyang Lin、King Chung Lam

  DOI：10.1039/b518232h

  日期：——

  The Sonogashira cross-coupling of 4,6-dichloro-2-pyrone with terminal acetylenes proceeds in good yields and high regioselectivity for the 6-position; dibenzylidene acetone (dba) type ligands play a non-innocent role in reactions mediated by Pd(dba)2/PPh3; theoretical studies indicate that C-6 oxidative addition is favoured both kinetically and thermodynamically.

  4,6-二氯-2-吡喃酮与末端炔烃的Sonogashira交叉偶联反应以良好产率和高度区域选择性进行，产物优先在6位生成；二苄叉丙酮（dba）型配体在Pd(dba)2/PPh3催化的反应中发挥着非无辜作用；理论研究表明，C-6的氧化加成在动力学和热力学上都更有利。
• Intramolecular Cyclization of Butadiyne Functionalized Ligands coordinated to Triosmium-Carbonyl Cluster
  作者：Avelina Arnanz、Rosa-María Medina、María-José Macazaga、Consuelo Moreno

  DOI：10.1002/zaac.201600229

  日期：2016.9

  Reactions between diynes and [Os3(CO)11(CH3CN)] in the presence of water give rise to the formation of intriguing hydride triosmium clusters [Os3(μ-H)(CO)9μ3,η1:η3:η1-RC2COHC≡CR}] (1a–1c) under mild conditions in high yields. When these allylic alcohol compounds 1a–1c are dissolved in dry polar and donor solvents, an intramolecular cyclization process takes place to give [Os3(μ-H)(CO)9μ3,η1:η3:η1-RC2CH=COCR}]

  二炔与[Os3(CO)11(CH3CN)]在水存在下的反应形成了有趣的氢化物三锇簇[Os3(μ-H)(CO)9μ3,η1:η3:η1-RC2COHC ≡CR}] (1a–1c) 在温和条件下高产。当这些烯丙醇化合物 1a-1c 溶解在干燥的极性和供体溶剂中时，会发生分子内环化过程，得到 [Os3(μ-H)(CO)9μ3,η1:η3:η1-RC2CH=COCR}] (2a-2c) 定量收率。利用[Os3(CO)11(CH3CN)]作为起始原料并加入水可以替代[Os3(μ-H)2(CO)10]的不便使用。这种合成方法为二炔环化提供了一种简便的途径，并且与迄今为止文献中描述的方法相比具有明显的优势。此外，类似的环化混合金属络合物 [Os3(μ-H)(CO)9μ3,η1:η3:
• Alkynyl-Bridged Ruthenium(II) 4′-Diferrocenyl-2,2′:6′,2′′-terpyridine Electron Transfer Complexes: Synthesis, Structures, and Electrochemical and Spectroscopic Studies
  作者：Kai-Qiang Wu、Jian Guo、Jian-Feng Yan、Li−Li Xie、Feng-Bo Xu、Sha Bai、Peter Nockemann、Yao-Feng Yuan

  DOI：10.1021/om200113d

  日期：2011.7.11

  The novel ligand 4′-diferrocenylalkyne-2,2′:6′,2′′-terpyridine (7; Fc-C≡C-Fc-tpy; tpy = terpyridyl; Fc = ferrocenyl) and its Ru2+ complexes 8–10 have been synthesized and characterized by single-crystal X-ray diffraction, cyclic voltammetry, and UV–vis and luminescence spectroscopy. Electrochemical data and UV absorption and emission spectra indicate that the insertion of an ethynyl group causes delocalization

  新型配体4'-二茂铁基炔-2,2'：6'，2''-吡啶（7 ;Fc-C≡C-Fc-tpy; tpy =吡啶基; Fc =二茂铁基）及其Ru 2+络合物8 –已经合成了10个，并通过单晶X射线衍射，循环伏安法，紫外可见光谱和发光光谱对其进行了表征。电化学数据以及UV吸收和发射光谱表明，乙炔基的插入会导致电子在扩展的π*轨道上离域。7的循环伏安测量显示两个连续的可逆的单电子氧化过程，半波电势分别为0.53和0.78V。Fe 2+的E 1/2值的微小变化Ru 2+离子配位后，/ Fe 3+氧化还原对表明Ru 2+和Fe 2+中心之间的相互作用较弱。插入乙炔基后，紫外可见吸收光谱显示1 [（d（π）Fe）6 ]→ 1 [（d（π）Fe）5（π* tpy Ru）的吸收峰出现红移。1 ] Ru 2+配合物的MMLCT 。在Ru 2+络合物8所呈现最强的发光强度（λ最大EM 712纳米，Φ EM相对于H
• Ferrocenyl-polyphenylenes: Toward Metallo-organic Polyaromatics
  作者：Dilwyn J. Roberts、Daniel J. Gregg、Chris M. Fitchett、Sylvia M. Draper

  DOI：10.1021/om100862a

  日期：2010.12.13

  form an eight-ring fused PAH supporting a ferrocene moiety (16-ferrocenyl(tribenzo[e;g,h,i;k])perylene (6)), the largest of its kind. The failure to generate further metallo-organic superaromatics is discussed in relation to the structure of the precursors and the oxidation of the ferrocene metal center. The synthesis of the polyphenylenes involves the [2+4] Diels−Alder reaction of phenyl, ferrocenyl

  这项工作继续了我们对取代的聚芳烃（PAHs）的研究。呈现被一个新的系列二茂铁基-取代的聚亚苯基，其中之一的成功路易斯酸催化的环化脱氢以形成八环稠合PAH支承二茂铁部分（16 -二茂铁基（三苯并[ ë ;克，ħ，我; ķ ]）per（6）），是同类产品中最大的。关于前体的结构和二茂铁金属中心的氧化，讨论了不能产生进一步的金属有机超芳族化合物的问题。聚亚苯基的合成涉及苯基，二茂铁基和氢封端的二茂铁基乙炔与四苯基环戊二烯酮的[2 + 4] Diels-Alder反应。描述并比较了所有系统的全光谱表征以及电子和氧化还原特性。还讨论了四苯基二茂铁基苯（1）（6的前体）的单晶X射线结构。