1,1'-bis[(benzo-1,3-dithiol-2-ylidene)methyl]ferrocene | 154987-99-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1,1'-bis[(benzo-1,3-dithiol-2-ylidene)methyl]ferrocene
• 英文别名: 1,1'-bis[(1,3-benzodithiol-2-ylidene)methyl]ferrocene；2-(cyclopenta-2,4-dien-1-ylmethylidene)-1,3-benzodithiole;iron(2+)
• CAS: 154987-99-2
• 化学式: C₂₆H₁₈FeS₄
• 分子量: 514.54
• InChiKey: XRMLSDQJFMPRJW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  1,1'-bis[(benzo-1,3-dithiol-2-ylidene)methyl]ferrocene 、 7,7,8,8-四氰基对苯二醌二甲烷 以 二氯甲烷 为溶剂， 以81%的产率得到
  参考文献：
  名称：

  新型电子给体化合物1,1'-双（苯并-1,3-二硫醇-2-亚烷基）二茂铁衍生物的合成及电化学性能

  摘要：

  基于1,3-二硫醇和二茂铁部分的强电子给体能力，合成了许多1,1'-双（苯并-1,3-二硫醇-2-亚基）二茂铁衍生物7a – b和12 – 14，新的π供体。这些化合物的结构和物理性质都通过实验技术和光谱分析进行了表征。这些新的供体化合物是基于Wittig-Horner反应的修饰以很高的收率获得的，并且1,3-二硫醇环被包括芳基-二茂铁基-芳基在内的共轭间隔基隔开。与DB-TTF 4相比，已研究了新化合物的电化学性质在室温下，使用Pt电极作为CH 2 Cl 2溶液中的工作电极，通过循环伏安法（CV）的类似物和母体二茂铁供体。观察到三个后续的氧化过程，因为三个氧化波仅与两个还原过程相关。的多晶样品14A - b处于导通状态σ室温14A =为0.2S厘米-1和σ室温14B = 4.8×10 -4小号厘米-1）分别，而化合物15和16，发现基本上如绝缘体（σ室温<10 - 10S cm -1）。

  DOI：

  10.1016/s0022-328x(03)00694-6
• 作为产物：
  描述：

  diethyl benzo[d][1,3]dithiol-2-yl-phosphonate 、 1,1'-二茂铁二甲醛 在 n-BuLi 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以75%的产率得到1,1'-bis[(benzo-1,3-dithiol-2-ylidene)methyl]ferrocene
  参考文献：
  名称：

  1,1'-Disubstituted Ferrocenes as Donors for Charge-Transfer Complexes. Synthesis, Structure, Conductivity, and Magnetic Properties

  摘要：

  Starting from ferrocene-1,1'-dicarbaldehyde (1), the novel electron donors 1,1'-bis[(5,6-dihydro-1,3-dithiolo[4,5b][1,4]dithiin-2-ylidene)methyl]ferrocene (5), 1,1'-bis[(1,3-benzodithiol-2-ylidene)methyl]ferrocene (6), and 1,1'-bis[2-[4-)methylthio)phenyl]-(E)-ethenyl]ferrocene (7) were prepared, and their electrochemical properties were studied. 5 and 6 undergo two reversible oxidation processes, whereas for 7 only the first electron removal is reversible in character. Crystals of 5 are monoclinic, space group P2(1)/c, with a = 12.448(1) angstrom, b = 12.178(1) angstrom, c = 16.219(1) angstrom, beta = 104.5(1)degrees, and Z = 4. In the solid state, molecules of 5 assume an eclipsed conformation, with the two substituents lying on top of each other (intramolecular stacking). 5 and 6 easily form 1:2 electron-transfer complexes with TCNQ (8 and 9, respectively), whereas 7 leads to a charge-transfer (CT) complex (10). Polycrystalline samples of 8 and 9 are conducting: sigma(rt)(8) = 0.26 S.cm-1 and sigma(rt)(9) = 0.20 S.cm-1. SQUID magnetic susceptibility measurements of 8 and 9 show these materials to undergo a phase transition dominated by a weak antiferromagnetic coupling (Curie-Weiss constants theta (8) = -3 K and theta (9) = -3 K). 10 is an insulator and is characterized by a very weak degree of electron transfer. Crystals of 10 are triclinic, space group P1BAR, with a = 7.796(1) angstrom, b = 8.607(1) angstrom, c = 16.396(2) angstrom, alpha = 92.88(1)degrees, beta = 97.83(1)degrees, gamma = 100.95(1)degrees, and Z = 1. In the CT complex 10, the donor 7 assumes an antiperiplanar conformation, thus leading to a 1D-DADA type structure.

  DOI：

  10.1021/om00016a027

文献信息

• Paramagnetic and Semiconducting 1:1 Salts of 1,1‘-Disubstituted Ferrocenes and [Ni(mnt)₂]^-. Synthesis, Structure, and Physical Properties
  作者：Markus Hobi、Stefan Zürcher,、Volker Gramlich、Urs Burckhardt、Christian Mensing、Michael Spahr、Antonio Togni

  DOI：10.1021/om9603981

  日期：1996.12.10

  The ferrocene-based electron donors 1,1'-bis[2-(4-(methylthio)phenyl)-(E)-ethenyl]ferrocene (2), 1,1'-bis[2-(4-methoxyphenyl)-(E)-ethenyl]ferrocene (3), 1,1'-bis[(1,3-dithiolo[4,5-b][1,3]dithiol-2-ylidene)methyl]ferrocene (4), and 1,1'-bis[(1,3-benzodithiol-2-ylidene)methyl]ferrocene (5) were found to react with ferrocenium bis(maleonitriledithiolato)nickelate (1-) ([FeCp(2)](+)[Ni(mnt)(2)](-), 6) to afford the corresponding 1:1 paramagnetic salts 7-10, containing 1,1'-disubstituted ferrocenium derivatives. SQUID magnetic susceptibility measurements of these new compounds showed a behavior dominated by antiferromagnetic interactions within pairs of [Ni(mnt)(2)](-) ions. Pressed pellets of compounds 7 ([2][Ni(mnt)(2)]) and 9 ([4][Ni(mnt)(2)]) are semiconducting, with a relatively large conductivity activation energy (0.85 and 1.13 eV). Crystals of 7 reveal the monodimensional nature of the compound. Each separate stack of [Ni(mnt)(2)](-) ions is flanked by two ferrocenium stacks. Ni-Ni distances alternate between 3.67 and 3.99 Angstrom.