1,1'-bis(ferrocenyldimethylsilyl)ferrocene | 152603-04-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,1'-bis(ferrocenyldimethylsilyl)ferrocene
• 英文别名: (η5-C5H5)Fe(η5-C5H4)SiMe2[(η5-C5H4)Fe(η5-C5H4SiMe2)](η5-C5H5)Fe(η5-C5H4)；FcSiMe2[(η5-C5H4)Fe(η5-C5H4SiMe2)]Fc；cyclopenta-1,3-diene;cyclopenta-1,4-dien-1-yl-cyclopenta-2,4-dien-1-yl-dimethylsilane;di(cyclopenta-2,4-dien-1-yl)-dimethylsilane;iron(2+)
• CAS: 152603-04-8
• 化学式: C₃₄H₃₈Fe₃Si₂
• 分子量: 670.388
• InChiKey: JQZAJSVLSKGMSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  39
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,1'-bis(ferrocenyldimethylsilyl)ferrocene 、 水 、 γ-cyclodextrin 以 二氯甲烷 、 水 为溶剂， 以33.8%的产率得到3(γ-cyclodextrin)*(1,1'-bis(ferrocenyldimethylsilyl)ferrocene)*40H2O
  参考文献：
  名称：

  Inclusion Complexation of Dimeric and Trimeric Oligo(ferrocenyldimethylsilanes) with γ-Cyclodextrin

  摘要：

  The oligo(ferrocenyldimethylsilanes) FcSiMe(2)Fc and FcSiMe(2)[(eta(5) -C5H4)Fe(eta(5)-C5H4SiMe2)]- Fc [Fe = (eta(5)-C5H5)Fe(eta(5)-C(5)H(4)A were encapsulated in gamma-cyclodextrin (CD) to give crystalline inclusion compounds with 2:1 and 3:1 (host-to-guest) stoichiometries, respectively. A complex between y-CD and ferrocene was also prepared for comparison. The formation of true inclusion complexes was confirmed in the solid state by powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), and C-13/Si-29 CP MAS NMR spectroscopy. Powder XRD reveals that the complexes containing ferrocene and the trimer 1,1'-bis(ferrocenyldimethylsilyl)ferrocene have very similar solid-state structures based on channel-type packing of the host molecules. The complexes containing the oligo(ferrocenyldimethylsilanes) dehydrate up to 100 degrees C, after which no mass loss is registered by TGA in the temperature range 100225 degrees C. The dissociation of the complexes occurs slightly above 225 degrees C and is immediately followed by the simultaneous release of the guests and the decomposition of the host in the temperature range 250-310 degrees C. C-13/Si-29 MAS NMR spectra of the inclusion compounds show that the encapsulation of the guest molecules in the CD cavity induces the host macrocycle to adopt a more symmetrical conformation, with each glucose unit in a more similar environment. The inclusion modes are discussed.

  DOI：

  10.1021/om050654m
• 作为产物：
  描述：

  monolithioferrocene 、 1,1'-bis(chlorodimethylsilyl)ferrocene 以 四氢呋喃 为溶剂， 以40%的产率得到1,1'-bis(ferrocenyldimethylsilyl)ferrocene
  参考文献：
  名称：

  (1,1'-Ferrocenediyl)ferrocenyl(methyl)silane, Its Thermally Ring-Opened Polymer, and Oligomer Models

  摘要：

  The synthesis and spectroscopic and structural characterization of a ferrocenyl-substituted silyl-[1]-ferrocenophane, (1,1'-ferrocenediyl)ferrocenyl(methyl)silane, 1, is reported. 1 crystallizes in space group P2(1)/c, with a = 20.344(8) Angstrom, b = 7.336(3) Angstrom, c 11.567(7) Angstrom, and beta 90.51(4)degrees. The dihedral angles between the two ferrocenophane cyclopentadienyl rings are 21.3 degrees, and the ring centroid-Fe-ring centroid angle is 164.3 degrees. Cyclic voltammetric analysis illustrates that both of the Fe centers, ferrocenyl and ferrocenophane, exhibit reversible redox behavior. This reversibility distinguishes the complex from other [1]-ferrocenophanes which exhibit irreversible oxidation under similar conditions. Thermal treatment of 1 results in facile polymerization to high molecular weight amorphous poly(ferrocenyleneferrocenyl(methyl)silane), 2. The molecular weight of the polymer was considerably increased by performing the polymerization in solution as opposed to the melt, M(w) = 210 000 vs 45 000. The electrochemical properties of the polymer indicate that neighboring Fe centers of the ferrocenylenesilane chain and pendant ferrocenyl groups interact, and four independent redox processes are observed. As a model for the ferrocenylenedialkylsilane polymers the synthesis and X-ray structure of 1,1'-bis(ferrocenyldimethylsilyl)ferrocene, 3, is also reported. 3 crystallizes in space group P2(1)/c, with a 10.084(2) Angstrom, b = 14.958(2) Angstrom, c 11.175(2) Angstrom, and beta = 114.98(1)degrees. The ferrocenyl and ferrocenylene units are perpendicular to each other, and each of the Fe units exhibits an individual redox process upon cyclic voltammetric investigation. Molecular mechanics calculations reveal a range of structures with local energy minima for such oligomers, one of which is equivalent to the single-crystal X-ray structure obtained for 3. The Fe-Fe distances in these conformers differ significantly, 6.1-6.9 Angstrom, suggesting that high molecular weight polymers also possess a range of possible conformations and inter-Fe Coulombic interactions.

  DOI：

  10.1021/om00021a043

文献信息

• Linear Oligo(ferrocenyldimethylsilanes) with between Two and Nine Ferrocene Units:  Electrochemical and Structural Models for Poly(ferrocenylsilane) High Polymers
  作者：Ron Rulkens、Alan J. Lough、Ian Manners、Sherri R. Lovelace、Casey Grant、William E. Geiger

  DOI：10.1021/ja962470s

  日期：1996.1.1

  of the prototypical high polymeric poly(ferrocenylsilane), poly(ferrocenyldimethylsilane) [Fe(η-C5H4)2SiMe2]n 6, three series of oligo(ferrocenylsilanes) R-fc-[SiMe2-fc]n-1-R‘ (fc = Fe(η-C5H4)2) 72−79 (R = R‘ = H), 82−87 (R = H and R‘ = SiMe3), and 92−97 (R = R‘ = SiMe3) have been prepared and studied (the subscript n in the oligomer refers to the number of ferrocene units present). These species were

  为了深入了解原型高分子聚（二茂铁基硅烷）、聚（二茂铁基二甲基硅烷）[Fe(η-C5H4)2SiMe2]n 6 的电化学和构象特性，三个系列的低聚（二茂铁基硅烷）R-fc-[SiMe2 -fc]n-1-R' (fc = Fe(η- )2) 72−79 (R = R' = H)、82−87 (R = H 和 R' = SiMe3) 和 92−97 (R = R' = SiMe3) 已被制备和研究（低聚物中的下标 n 是指存在的二茂铁单元的数量）。这些物质是通过硅桥联 [1] 二茂铁 Fe(η- )2SiMe2 5 的阴离子开环低聚反应制备的。 用二茂铁基锂 FcLi (Fc = Fe(η-C5H5)(η- )) 引发，然后用 H2O 或 SiMe3Cl 淬灭分别得到 H-fc-[SiMe2-fc]n-1-H (72-9) 或 H-fc-[SiMe2-fc]n-1-SiMe3 (82-7)。
• Experimental and Theoretical Study of the Encapsulation of a Linear Oligo(ferrocenylsilane) Trimer with β‐Cyclodextrin
  作者：José A. Fernandes、Sérgio Lima、Susana S. Braga、Martyn Pillinger、José E. Rodríguez‐Borges、Paulo Ribeiro‐Claro、José J. C. Teixeira‐Dias、Isabel S. Gonçalves

  DOI：10.1002/ejic.200500551

  日期：2005.12

  An inclusion compound comprising β-cyclodextrin (β-CD) and the trimetallic oligo(ferrocenylsilane) FcSiMe2[(η5-C5H4)Fe(η5-C5H4SiMe2)]Fc [Fc = (η5-C5H5)Fe(η5-C5H4)] has been prepared and characterised in the solid state by elemental analysis, powder X-ray diffraction, thermogravimetric analysis and magic angle spinning NMR spectroscopy (13C, 29Si). The results are consistent with the formation of a

  包含β-环糊精（β-CD）和三金属低聚（二茂铁基硅烷）FcSiMe2[(η5-C5H4)Fe(η5- SiMe2)]Fc[Fc = (η5-C5H5)Fe(η5- )]的包合物具有通过元素分析、粉末 X 射线衍射、热重分析和魔角旋转 NMR 光谱 (13C, 29Si) 在固态下制备和表征。结果与 2:1（宿主对客体）包合物的形成一致。为了研究可能的夹杂物几何形状，进行了从头算计算。对于二茂铁碎片相对于 β-CD 轴（= 29°）的倾斜几何形状，在边缘平面下方包含 140 pm 的相应 Fe 中心时，获得了最佳的主客体拟合。有机金属三聚体的结构允许它与第二个 β-CD 宿主相互作用，导致 2：1 化学计量。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Anionic ring-opening oligomerization and polymerization of silicon-bridged [1]ferrocenophanes: Characterization of short-chain models for poly(ferrocenylsilane) high polymers
  作者：Ron Rulkens、Alan J. Lough、Ian Manners

  DOI：10.1021/ja00081a062

  日期：1994.1