diferrocenylmethylsilane | 931127-23-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: diferrocenylmethylsilane
• 英文别名: cyclopenta-1,3-diene;di(cyclopenta-2,4-dien-1-yl)-methylsilane;iron(2+)
• CAS: 931127-23-0
• 化学式: C₂₁H₂₂Fe₂Si
• 分子量: 414.185
• InChiKey: YNPYUJPUFYVTIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  烯丙基三乙氧基硅烷 、 diferrocenylmethylsilane 在 铂(0)-1,3-二乙烯-1,1,3,3-四甲基二硅氧烷 作用下， 以 甲苯 为溶剂， 反应 12.08h， 以90%的产率得到((diferrocenylmethylsilyl)propyl)triethoxysilane
  参考文献：
  名称：

  Synthesis and Electrochemistry of ((Diferrocenylsilyl)propyl)- and ((Triferrocenylsilyl)propyl)triethoxysilanes

  摘要：

  Triferrocenylsilane 2 was synthesized. Hydrosilylation reactions employing allyltriethoxysilane and diferrocenylmethylsilane (1) and triferrocenylsilane (2) yielded new ferrocenyltriethoxysilane compounds functionalized with two (3) and three (4) interacting ferrocenyl units, respectively. Characterization of 2 and the ethoxysilane derivatives 3 and 4 by elemental analysis, H-1, C-13{H-1}, and Si-29{H-1} NMR spectroscopy, and mass spectrometry supports their assigned structures. The crystal structure of 2 has been determined by a single-crystal X-ray diffraction study. The redox activity of the ferrocenyl centers in 2-4 has been characterized by cyclic voltammetry and square wave voltammetry in dichloromethane containing [n-Bu4N] [PF6] or [n-Bu4N][B(C6F5)(4)] as electrolyte support. Voltammetric studies of 2-4 in solution exhibit the pattern of communicating ferrocenyl sites with two or three distinct, separated oxidation waves. Platinum oxide surfaces are covalently modified by redox-active 3 and 4.

  DOI：

  10.1021/om400387c
• 作为产物：
  描述：

  甲基二氯硅烷 、 二茂铁 在 potassium tert-butylate 、 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 0.5h， 以66%的产率得到diferrocenylmethylsilane
  参考文献：
  名称：

  二茂铁稳定的硅离子家族：合成，29Si NMR表征，路易斯酸度，取代基加扰和量子化学分析

  摘要：

  进行系统的实验和理论研究的目的是深入了解二茂铁稳定的硅离子作为硅原子上取代基的函数的独特键合情况，并了解决定29 Si NMR化学位移和亲电性的结构参数这些强路易斯酸。为此，通过硅烷与三苯甲基阳离子的氢化物抽象反应制备了二茂铁稳定的硅阳离子家族的十个新成员，并以多核 1 H和29为特征Si NMR光谱。仔细观察NMR谱图可以发现，其他次要信号不是杂质，而是取代模式与最初形成的阳离子不同的甲硅烷基离子。这些信号的仔细分配提供了实验证明，即受空间影响较小的甲硅烷基离子能够与未反应的硅烷前体交换取代基。密度泛函理论计算提供了对取代基转移的机理性见解，其中迁移基团在涉及二茂铁桥接中间体的协同过程中在两个硅片段之间交换。此外，对29 Si NMR化学位移的量子化学分析揭示了δ（29Si）值和硅阳离子子集的Fe⋅⋅⋅Si距离。电子本地化功能和电子本地化指标分析显示，铁，硅和C'ipso原子之间存在一个

  DOI：

  10.1002/chem.201302885

文献信息

• Carbosilane based dendritic cores functionalized with interacting ferrocenyl units: synthesis and electrocatalytical properties
  作者：José Losada、Pilar García-Armada、Víctor Robles、Ángel M. Martínez、Carmen M. Casado、Beatriz Alonso

  DOI：10.1039/c1nj20190e

  日期：——

  The reaction of bis(ferrocenyl)methylsilane 1 with two carbosilane dendritic cores containing terminal allyl units gives dendrimers functionalized with eight interacting ferrocenyl units. They show two reversible ferrocenyl waves in cyclic voltammetry (CV) and form derivatized Pt electrodes. Platinum electrodes modified with electrodeposited films of these two dendrimers exhibit electrocatalytic activity towards the reduction of oxygen and both oxidation and reduction of hydrogen peroxide. The molecular structure of 1 has been determined by single-crystal X-ray diffraction studies.

  双(二茂铁基)甲基硅烷 1 与含有末端烯丙基单元的两个碳硅烷树枝状核心反应，生成了具有八个相互作用二茂铁基单元的树枝状聚合物。它们在循环伏安法（CV）中显示出两个可逆的二茂铁波，并形成了衍生化的铂电极。用这两种树枝状聚合物的电沉积薄膜修饰的铂电极对氧气的还原以及过氧化氢的氧化和还原具有电催化活性。通过单晶 X 射线衍射研究确定了 1 的分子结构。
• Ferrocenyl Dendrimers Based on Octasilsesquioxane Cores
  作者：Marta Herrero、Beatriz Alonso、José Losada、Pilar Garcı́a-Armada、Carmen M. Casado

  DOI：10.1021/om300591p

  日期：2012.9.10

  bis(ferrocenyl)methylsilane (1) give dendrimers functionalized with 16 (G1-Fc16) and 32 (G2-Fc32) interacting ferrocenyl units. Characterization of the dendrimers by 1H, 13C1H}, and 29Si1H} NMR spectroscopy as well as mass spectrometry supports their assigned structures. The thermal behavior of dendrimers G1-Fc16 and G2-Fc32 was studied by TGA techniques. The redox activity of the ferrocenyl centers

  两个含有末端乙烯基的八硅倍半氧烷树状核与双（二茂铁基）甲基硅烷（1）的氢化硅烷化反应得到被16（G1-Fc 16）和32（G2-Fc 32）相互作用的二茂铁单元官能化的树状聚合物。通过1 H，13 C 1 H}和29 Si 1 H} NMR光谱以及质谱对树枝状聚合物的表征支持了它们的指定结构。通过TGA技术研究了树枝状聚合物G1-Fc 16和G2-Fc 32的热行为。G1-Fc中二茂铁基中心的氧化还原活性在含有[ n- Bu 4 N] [PF 6 ]作为电解质载体的二氯甲烷中，通过循环伏安法和方波伏安法表征了图16和G2-Fc 32的特征。树枝状聚合物G1-Fc 16和G2-Fc 32的溶液伏安研究显示了二茂铁基位点与两个不同的分离的氧化波连通的模式。树枝状聚合物也沉积在电极表面上，并通过CV对电极进行了研究，显示出形成电活性膜的前景十分广阔，可用于将这些材料用于生物传感器的开发。
• Ferrocene-Stabilized Silicon Cations as Catalysts for Diels–Alder Reactions: Attempted Experimental Quantification of Lewis Acidity and ReactIR Kinetic Analysis
  作者：Alexander R. Nödling、Kristine Müther、Volker H. G. Rohde、Gerhard Hilt、Martin Oestreich

  DOI：10.1021/om401040y

  日期：2014.1.13

  The Si-29 NMR chemical shifts of ferrocene-stabilized silicon cations span a wide range depending on the substituents at the silicon atom. These pronounced differences in deshielding of the silicon atom do not translate into significant differences in their catalytic activity in Diets-Alder reactions. It was shown by Lewis pair formation with Lewis base probes (Et3PO and pyridine-d(5)) that there is hardly any difference between these silicon cations after coordination to a Lewis base. This finding not only thwarts experimental quantification of the Lewis acidity of the free Lewis acids but also demonstrates that the reactivity differences are largely due to steric effects for a given counteranion. These observations are further verified by a ReactIR kinetic analysis. The Lewis acidity of silicon cations and their performance as catalysts cannot be correlated with Si-29 NMR chemical shifts as well as resonances of adducts with Lewis base probes, not even for a subset of silicon Lewis acids.
• Electrochemical and bioelectrocatalytical properties of novel block-copolymers containing interacting ferrocenyl units
  作者：M.P. García Armada、J. Losada、F.J. López-Villanueva、H. Frey、B. Alonso、C.M. Casado

  DOI：10.1016/j.jorganchem.2008.05.038

  日期：2008.8

  The electrochemical characterization of three different polystyrene-b-polybutadiene block-copolymers, functionalized with diferrocenylsilane units, is reported. The PB-blocks have been functionalized with different fractions of electronically communicated, PSm-PBn (p) (HSiMeFc(2))(p) units, where m = 615, n = 53, p = 39 (1), m = 375, n = 92, p = 76 (2) and m = 455, n = 204, p = 170 (3). Electrochemical characterization has been carried out both in solution and after electrochemical deposition onto platinum electrodes. The bioelectrocatalytical properties of electrodes modified with the polymers in the nicotinamide dinucleotide (NADH) and glucose oxidase (GOx) oxidations have been investigated as a function of the constitution and structure of the polymers. The analytical properties of electrodes modified with these polymers as sensors of NADH and GOx are described. In addition, an amperometric biosensor for glucose, prepared by electrostatic immobilization of glucose oxidase onto a platinum electrode modified with one of the ferrocenyl block-copolymers as an example, has been developed. (c) 2008 Elsevier B. V. All rights reserved.