2,5-bis(ferrocenylethynyl)thiophene | 261622-36-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2,5-bis(ferrocenylethynyl)thiophene
• 英文别名: 2,5-bis(2-cyclopenta-2,4-dien-1-ylethynyl)thiophene;cyclopenta-1,3-diene;iron(2+)
• CAS: 261622-36-0
• 化学式: C₂₈H₂₀Fe₂S
• 分子量: 500.227
• InChiKey: QKWLHVKUEZMJOV-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：

  2,5-bis(ferrocenylethynyl)thiophene 、 四氰基乙烯 以 二氯甲烷 为溶剂， 反应 2.0h， 以90%的产率得到2,5-bis(1,1,4,4-tetracyano-2-ferrocenyl-1,3-butadien-3-yl)thiophene
  参考文献：
  名称：

  通过芳基，联芳基和三芳基间隔基连接的1,1,4,4-四甲基--2-二茂铁基-1,3-丁二烯的合成，性质和氧化还原行为

  摘要：

  芳基取代的1,1,4,4-四氰基-1,3-丁二烯（FcTCBDs）和双（1,1,4,4-四氰基丁二烯）（bis-FcTCBDs）在每个末端均具有二茂铁基。通过在[2 + 2]环加成反应中各种炔烃与四氰基乙烯（TCNE）的反应制备，然后对最初形成的[2 + 2]环加合物（即环丁烯衍生物）进行逆电环化。通过使用紫外/可见光谱研究了供体（二茂铁）和受体（TCBD）部分之间的特征分子内电荷转移（ICT）。通过循环伏安法（CV）和微分脉冲伏安法（DPV）检查了FcTCBD和bis-FcTCBD的氧化还原行为，这揭示了它们根据二茂铁和TCBD部分的数量进行多电子转移的特性。而且，

  DOI：

  10.1002/chem.201405004
• 作为产物：
  描述：

  2,5-二溴噻吩 、 二茂铁乙炔 在 CuI 、 Pd(PPh₃)2Cl₂ 作用下， 以 二乙胺 为溶剂， 以77%的产率得到2,5-bis(ferrocenylethynyl)thiophene
  参考文献：
  名称：

  Biferrocenes with Heteroaromatic Spacers:  Synthesis, Structure, and Electrochemistry

  摘要：

  DOI：

  10.1021/om9908635

文献信息

• Synthesis, structures and properties of platinum(ii) complexes of oligothiophene-functionalized ferrocenylacetylene
  作者：Wai-Yeung Wong、Guo-Liang Lu、Ka-Fai Ng、Ka-Ho Choi、Zhenyang Lin

  DOI：10.1039/b105016h

  日期：2001.11.14

  A series of rigid-rod alkynylferrocenyl precursors with oligothiophene (from thiophene to terthiophene) linkage units in the backbone, [(η5-C5H5)Fe(η5-C5H4)CC(C4H2S)mBr] 2a–2c, [(η5-C5H5)Fe(η5-C5H4)CC(C4H2S)mCCSiMe3] 3a–3c and [(η5-C5H5)Fe(η5-C5H4)CC(C4H2S)mCCH] 4a–4c (m = 1–3), have been prepared in moderate to good yields. The ferrocenylacetylene complexes 4a–4c can be used to form a range of stable platinum(II) alkynyl and bis(alkynyl) compounds trans-[(η5-C5H5)Fe(η5-C5H4)CC(C4H2S)mCCPt(PEt3)2Ph] 5a–5c and trans-[(η5-C5H5)Fe(η5-C5H4)CC(C4H2S)mCCPt(PBu3)2CC(C4H2S)mCC(η5-C5H4)Fe(η5-C5H5)] 6a–6c (m = 1–3). All these new compounds have been fully characterized by analytical and spectroscopic methods and the molecular structures of the bithienyl-linked complexes [(η5-C5H5)Fe(η5-C5H4)CC(C4H2S)2CC(η5-C5H4)Fe(η5-C5H5)], 2b, 4b, 5b and 6b have been established by X-ray crystallography. Structural analysis of 6b confirms its rigid-rod structural motif, featuring coplanar bithienyl rings and a trans arrangement of the two bithiophene groups. An iron–iron through-space distance of ca. 32 Å is observed in 6b. Although there is no significant metallocene–metallocene interaction through the alkynyl–platinum–oligothiophene bridge, a slight negative shift of the ferrocene–ferrocenium redox potential in the platinum-containing species indicates some degree of electron delocalization into the platinum segment, in line with the results from theoretical studies. Oxidation of the thiophene units is facilitated by the presence of the platinum centre and increased conjugation in the chain.

  一系列具有刚性结构的主链含噻吩链联接单元(-(C$_4}$H$_2}$S)$_m$-Br, m=1~3)的炔基二茂铁前驱体[(η$^5$-C$_5}$H$_5$)Fe(η$^5$-C$_5}$H$_4}$)CC(C$_4}$H$_2}$S)$_m$Br]2a–2c, [(η$^5$-C$_5}$H$_5$)Fe(η$^5$-C$_5}$H$_4}$)CC(C$_4}$H$_2}$S)$_m$CCSiMe$_3}$]3a–3c 和 [(η$^5$-C$_5}$H$_5$)Fe(η$^5$-C$_5}$H$_4}$)CC(C$_4}$H$_2}$S)$_m$CCH]4a–4c 已被合成并分离得到中等到良好的收率。炔基二茂铁配合物4a–4c 可以用来合成一系列稳定的含 Pt(II)炔基和双炔基化合物trans-[(η$^5$-C$_5}$H$_5$)Fe(η$^5$-C$_5}$H$_4}$)CC(C$_4}$H$_2}$S)$_m$CCPt(PEt$_3}$)$_2$Ph]5a–5c，和 trans-[(η$^5$-C$_5}$H$_5$)Fe(η$^5$-C$_5}$H$_4}$)CC(C$_4}$H$_2}$S)$_m$CCPt(PBu$_3}$)$_2$CC(C$_4}$H$_2}$S)$_m$CC(η$^5$-C$_5}$H$_4}$)Fe(η$^5$-C$_5}$H$_5$)]6a–6c (m = 1~3)。所有这些新化合物经由分析和光谱方法进行了全面的鉴定，双噻吩联接配合物[(η$^5$-C$_5}$H$_5$)Fe(η$^5$-C$_5}$H$_4}$)CC(C$_4}$H$_2}$S)$_2$CC(η$^5$-C$_5}$H$_4}$)Fe(η$^5$-C$_5}$H$_5$)]的 2b, 4b, 5b 和 6b 的分子结构由 X-射线单晶衍射法确立。结构分析确认 6b 具有刚性棒结构， 特征为双噻吩环共面与双噻吩基团顺式排列。在 6b 中观察到铁—铁之间空间的距离为 3.2 Å。虽然没有通过炔基—铂—噻吩链检测到明显的金属茂-金属茂相互作用，在含铂化合物中二茂铁-二茂铁正离子的氧化还原电位小负移表明有某种程度的电子离域到铂片段，与由理论研究得到的结果相一致。在链中增加的共轭及由于存在铂中心使噻吩单元易于被氧化。
• Cationic (η⁶-Arene)tricarbonylmanganese Linked to Ferrocene Complexes
  作者：Béatrice Jacques、Jean-Philippe Tranchier、Françoise Rose-Munch、Eric Rose、G. Richard Stephenson、Carine Guyard-Duhayon

  DOI：10.1021/om034168f

  日期：2004.1.1

  exa-2,4-dienyl)]tricarbonylmanganese(I) (2) and 2-bromo-5-[η5(1−5)-(4-methoxycyclohexa-2,4-dienyl]tricarbonylmanganese(I)}thiophene (13) with the ethynylferrocene derivative 5 give the dinuclear complexes 1-(ferrocenylethynyl)[η5(1−5)-(4-methoxycyclohexa-2,4-dienyl)]tricarbonylmanganese(I) (6) and 2-(ferrocenylethynyl)-5-[η5(1−5)-(4-methoxycyclohexa-2,4-dienyl)tricarbonylmanganese]thiophene (10).

  钯催化的Sonogashira偶联中性[η的反应5（1-5） - （1-氯-4- methoxycyclohexa -2,4-二烯基）] tricarbonylmanganese（I）（2）和2-溴-5 - [ η 5（1-5） - （4- methoxycyclohexa -2,4-二烯基] tricarbonylmanganese（I）}噻吩（13）与所述ethynylferrocene衍生物5得到双核配合物1-（ferrocenylethynyl）[η 5（1-5） - （4- methoxycyclohexa -2,4-二烯基）] tricarbonylmanganese（I）（6）和2-（ferrocenylethynyl）-5- [η 5（1-5） - （4- methoxycyclohexa -2,4-二烯基）tricarbonylmanganese ]噻吩（10）。类似地
• Carborane bridged ferrocenyl conjugated molecules: synthesis, structure, electrochemistry and photophysical properties
  作者：Jian-Feng Yan、Gai-Ge Zhu、Ye Yuan、Cai-Xia Lin、Shu-Ping Huang、Yao-Feng Yuan

  DOI：10.1039/d0nj00826e

  日期：——

  The reaction between alkynyl bridged bisferrocenyl derivatives and decaborane results in new symmetrical ferrocenyl substituted carboranes 8–11. All the new compounds have been identified and fully characterized by means of NMR and HRMS. The molecular structures of target compounds 8–11 were determined by single-crystal X-ray analysis. The electrochemistry studies of the ferrocenyl substituted carboranes

  炔基桥联的双二茂铁基衍生物与十硼烷之间的反应产生新的对称的二茂铁基取代的碳硼烷8-11。所有新化合物均已通过NMR和HRMS进行了鉴定和充分表征。目标化合物8-11的分子结构通过单晶X射线分析确定。报道了二茂铁基取代的碳硼烷的电化学研究，结果表明，在这些对称的共轭低聚物中，两个二茂铁基之间存在大量电子通讯。混合价物质的热力学稳定性以11 < 8 < 10 < 9的顺序增加。
• Synthesis and characterisation of aromatic ethynyl-bridged ferrocenes
  作者：Nazia Chawdhury、Nicholas J. Long、Mary F. Mahon、Li-ling Ooi、Paul R. Raithby、Stephanie Rooke、Andrew J.P. White、David J. Williams、Muhammad Younus

  DOI：10.1016/j.jorganchem.2003.11.035

  日期：2004.2

  A series of aromatic ethynyl-bridged ferrocenes with the general formula Fc-CdropC-R-CdropC-Fc (Fc = ferrocenyl, R = C6H2(-p-CH3)(2) (1), C6H4-p-C6H4 (2), C5H3N (3), 9,10-C14H8 (4), C4H2S (5), (C4H2S)(2) (6) and (C4H2S)(3) (7)) has been synthesised by the reaction of ethynyl ferrocene with the appropriate dibromo-arenes. The new complexes have been characterised by spectroscopic techniques. The structures of 3 and 7 were determined via X-ray crystallography, and both show the trans-trans configuration of the two ethynyl ferrocene groups with respect to the central R group. The electronic properties of the compounds have been studied via optical spectroscopy and cyclic voltammetry. (C) 2004 Elsevier B.V. All rights reserved.
• The influence of an ethynyl spacer on the electronic properties in 2,5-ferrocenyl-substituted heterocycles
  作者：Ulrike Pfaff、Alexander Hildebrandt、Marcus Korb、Heinrich Lang

  DOI：10.1016/j.poly.2014.02.008

  日期：2015.1

  A series of binuclear complexes based on five-membered heterocycles featuring alkynyl ferrocenyl groups, 2,5-(FcC equivalent to equivalent to C)(2)-(C4H2E)-C-c (E = NPh, 3a; S. 3b; O, 3c), has been synthesized using the Sonogashira C,C cross-coupling protocol. The molecular structures of 3a and 3c in the solid state are discussed. The influence of the ethynyl unit on the electronic and (spectro)electrochemical properties of these compounds is shown by cyclic voltammetry (CV), square wave voltammetry (SWV) and in situ UV-Vis-NIR and IR spectroscopy. The high Delta E-p values (140-204 mV) of the single reversible redox events indicate that two individual oxidation processes take place in a close potential range. Nevertheless, the NIR measurements indicate weak and broad intervalence charge transfer (IVCT) absorptions for the mixed-valent monocationic species 3a-c(+). Compared to 2,5-Fc(2)-(C4H2E)-C-c (E = NPh, S, O) the absorptions for the IVCT transitions are shifted hypsochromically, showing that the charge transfer process is promoted at higher excitation energies, due to larger metal-metal distances in 3a-c. The occurrence of IVCT absorptions demonstrates that the 2,5-diethynylferrocenyl heterocycles are class II systems according to Robin and Day. (C) 2014 Elsevier Ltd. All rights reserved.