二茂铁及其应用

本文扼要介绍了二茂铁这一金属有机化合物的性质、制备方法及其在工业生产各个领域的应用。1951年,T.J.Kealy等人利用环戊二烯溴化镁同无水三氯化铁反应,     

二茂铁的制备及应用

1　概述二茂铁又叫双环戊二烯基铁 ,是以石油化工中Ｃ5 馏分中的环戊二烯为原料合成出来的一种具有芳香族性质的有机过渡金属化合物 ,分子式Ｆｅ(Ｃ5Ｈ5) 2 ,分子量 1 86,外观为橙黄色针状结晶 ,熔点 1 73～ 1 74℃ ,沸点 2 4 9℃ ,1 0 0℃以上能升华 ;不溶于水 ,溶于甲醇、乙醇、乙醚、石油醚、二氯甲烷、苯等有机溶剂 ,其分子呈极性 ,具有高度热稳定性、化学稳定性和耐辐射性 ,溶于浓硫酸中 ,在沸腾的烧碱溶液和盐酸中不溶解 ,不分解。二茂铁在化学性质上与芳香族化合物相似 ,不容易发生加成反应 ,容易发生二茂铁环上的亲电取代反应 ,如金…     

二茂铁丙烯酰氯的合成

我们曾报道了二茂铁丙烯酰氯及其酰胺衍生物的合成 [1] ,但实验中只得到了酰氯的粗品 ,未能表征。同时收率也只有 35 %。以后的多次实验发现 ,以60～ 90°C的无水石油醚作反应溶剂代替前文报道的无水苯 ,溶剂易除 ,产物易结晶 ,得到纯度较高的暗红色片状晶体 ,mp:76～ 78°C,产率可达 45 %。以元素分析 ,红外光谱确证其结构。合成路线如下 :Fc H DMF,POCl3CHCl3Fc CHO+ CH2 ( COOH) 2六氢吡啶吡啶H+ Fc CH =CHCOOH + SOCl2吡啶石油醚(美国 Nicolet公司 )。所用试剂均为分析纯或化学纯 ;石油醚经金属钠回流重蒸 ,二氯亚砜使用…     

1,1'-二甲基二茂铁合成新方法的研究

近年来二茂铁及其衍生物的合成与应用研究成为金属有机化学界研究的热点问题,标题化合物就是一类重要的二茂铁衍生物,它在催化合成、生物学、医学等领域表现出越来越重要的作用。考察了标题化合物的几种合成路线,开发了一条反应条件温和、反应试剂易得、产率较高的新路线,成功地合成了目标产物,并对其进行了熔点和1HNMR分析。     

二（1`—乙酰基）二茂铁基丙二酮的合成

二(1′-乙酰基)二茂铁基丙二酮的合成方法;元素分析及IR红外特征吸收;化合物的物理性质。     

二茂铁及其提纯工艺

1 二茂铁 1.1 二茂铁的合成二茂铁的合成有不少报道,合成工艺较成熟。目前国内已有许多厂家批量生产,实验室制备一般采用如下两种方法:     

二茂铁基丁二烯的合成

参照文献上改进的瑞氏反应法,以石墨为载体,以由钾还原氯化锌得到的活性锌作为瑞氏反应的催化剂,一步合成了二茂铁基丁二烯。产率85%。     

(二茂铁基、乙基二茂铁基)甲基丁胺的合成与表征

（二茂铁基、乙基二茂铁基）甲醇与BF3在二氯甲烷中作用，形成相应的双二茂铁甲基碳正离子，无需从反应混合物中分离出来，该离子便可与正丁胺作用得到标题化合物，由元素分析、红外光谱确认了该化合物的结构。     

二茂铁的定量分析—比色法

本文介绍用比色法定量分析二茂铁,减少了运算误差,分析准确而快速。一、前言二茂铁也叫环戊二烯铁,是一种金属有机化合物,分子式:(C_5H_5)     

电解法合成二茂铁

详细阐述了几种电解法合成二茂铁的生产技术和它们的优缺点。     

Ferrocene pincer ligands made easy

A simple and effective two step synthesis of ferrocene pincer ligands is described starting from readily available N,N-dimethylaminomethylferrocene.     

二茂铁的电解合成及应用

二茂铁(Ferrocene)是一种有着广泛用途的金属有机化合物.自20世纪50年代首次发现以来,由于其特殊的化学结构,引起了众多化学家的兴趣,数百种的二茂铁衍生物被制备出来,并应用到各个领域之中.目前,合成二茂铁的主要方法是化学合成法和电化学合成法两种.阐述了二茂铁的性质、二茂铁及衍生物的应用、二茂铁的电解合成及影响因...     

Novel Organometallic Aromatic Azo Polyesters Based on Ferrocene

Some ferrocene containing aromatic azo polyesters were prepared by condensing 1,1-ferrocenedicarbonyl chloride with different azo groups containing aromatic diols, which were synthesized by diazotization coupling reaction from aromatic diamines. The polymeric products were separated as two portions on the basis of their solubility and subsequently characterized by their elemental analysis and FTIR spectral studies. Thermal properties of the products were measured by differential scanning calorimetry and thermogravimetry and the activation energies of pyrolysis were calculated using Horowitz and Metzger's method. The molecular weights of the soluble portions were determined by gel permeation chromatography (GPC) and these portions were also characterized by their inherent viscosities and UV-Vis spectroscopic studies.     

Ferrocene sulfonates as electrocatalysts for sulfide detection

The electrochemical characterization of both the mono- and di-substituted forms of ferrocene sulfonate are given. The results show both species produce voltammograms consistent with quasi-irreversible diffusion controlled redox reactions. The FcSO₃⁻ species was found to be easier to oxidize than its Fc(SO₃)₂²⁻ counterpart, due to the electron withdrawing affect of the sulfonate group on the Fe centre.In the presence of sulfide, the voltammetric response of FcSO₃⁻ is shown to be consistent with the occurrence of an electrocatalytic EC′ reaction. This analytical response was utilized as a means of determining sulfide and was found to be linear over the concentration 0.02-1 mM with a limit of detection of 14 μM.     

New Molecular Wires with Two Ferrocene Hinges

Conventional molecular wires of the oligophenyleneethynylene (OPE) type are two-dimensional rigid molecules of fixed length. Possible problems concerning π,π stacking and device geometry associated therewith might be overcome by replacement of some of the 1,4-phenylene moieties by 1,1′-disubstituted ferrocene units. These make the wire three-dimensional thereby reducing the likelihood of intermolecular π,π interactions and serve in addition as hinges as a result of the almost free rotation around the Cp-Fe-Cp axis. This feature provides a limited conformational flexibility with the possibility of a length adjustment comparable to a foldable ruler. Here the syntheses and some physical properties of molecular wires containing two ferrocene hinges are described. In a number of cases the Sonogashira coupling reactions used for the coupling of the respective building blocks proceed much faster under microwave irradiation as compared to conventional heating. This paper is dedicated to Professor Didier Astruc in honor of his pioneering research efforts and accomplishments in the field of organometallic materials.     

Preparation of Triazole-furnished Ferrocene Derivatives and their Polymer Complexes of Silver(I)

Condensation reactions of feroccenemethanol and of 1,1′-feroccenedimethanol with benzotriazole and triazole produce the ferrocene derivatives with one or two N-azole-containing substituents bonded to the cyclopentadienyl ligands. The bifunctional ferrocene derivatives, 1,1′-bis[(1,2,3-benzotriazol-1-yl)methyl]ferrocene and 1,1′-bis(1,2,4-triazoyl)ferrocene, reacts with [Ag(MeCN)₄]PF₆ to cause separation of the macromolecular complexes from the solution. The former ferrocene derivative with benzotriazole groups yields the complex of Ag(I) with Ag:ligand = 2:3. The Ag center is bonded to three triazole groups, forming a trigonal structure. Crystals of the complexes contain the ladder-shaped sheets formed by Ag(I) and the ligand, and these sheets are aligned in a staggered fashion. The latter ligand with 1,2,4-triazole groups and Ag(I) yield the 1:1 complex. Counter anions and MeCN molecules are contained within holes formed by the Ag(I) centers bonded with a metal–metal bond and the bifunctional ligands. NMR and UV measurement of the MeCN solution of these macromolecular complexes revealed dissociation of the ligand and degradation of the complexes in solution. This paper is dedicated to Professor Takakazu Yamamoto in honor of his pioneering research efforts and accomplishments in the fields of organometallics and π-conjugated polymers.     

二茂铁的加入对铝碳耐火材料性能的影响

研究了二茂铁加入铝碳耐火材料中后,铝碳耐火材料性能的变化.与仅添加Si和Al试样的性能相比,添加二茂铁的试样的强度,抗氧化性明显增大,且二茂铁的含量为1%～3%左右时,复合添加Si、Al和二茂铁的试样的强度及抗氧化性均有较大提高.     

Radical Polymerization of Methyl Methacrylate in Presence of Ferrocene. Monte Carlo Simulation

Abstract

Monte-Carlo technique is used for the numerical simulation of radical polymerization kinetics of methyl methacrylate in the presence or absence of ferrocene and exposition of molecular-weight distribution during the process. The peculiarities of polymeric radical concentration changes at the initial stage of polymerization are shown. Satisfactory correspondence between calculated and experimental data is obtained. The data of numerical experiment have allowed to evaluate the influence of ferrocene on kinetic parameters of polymerization.     

Synthesis and Characterization of Ferrocene-Containing Hyperbranched Poly(aroylarylene)s

Ferrocene-containing hyperbranched poly(aroylarylene)s are prepared in satisfactory yields by one-pot copolycyclotrimerization of bis(aroylacetylene)s with a ferrocene-containing monoyne. The ferrocene content of the polymers can be varied by changing the monomer feed ratio, and copolymers with up to 41 mol% of ferrocene moiety can be readily prepared. All the polymers are thermally stable, losing little of their weights when heated to 340 °C. This article is dedicated to Professor Didier Astruc.     

Evaluation of 4‐(Dimethylsilyl) Butyl Ferrocene Grafted HTPB as a Burning Rate Modifier in Composite Propellant Formulation using Bicurative System

High burning rate composite propellants are achieved by incorporation of fine particles of oxidizer, transition metal oxides, and liquid ballistic modifiers. However, they pose processing problems, inertness to the composition and migration related issues. To overcome such problems, an attempt was made to incorporate ferrocenyl grafted HTPB as a burning rate modifier by partly replacing HTPB from 10 % to 50 % using TDI/ IPDI bicurative system and to study their processability in terms of viscosity, mechanical, thermal, sensitivity, and ballistic properties. The data on viscosity reveal that there is a marginal enhancement in end of mix viscosity as percentage of ferrocenyl grafted HTPB increases. The mechanical data reveal that tensile strength and elastic modulus increases, whereas percentage elongation decreases compared to base composition. The results on thermal properties infer that, as the percentage of ferrocenyl grafted HTPB increases, onset decomposition temperature decreases. The impact and friction sensitivity data also envisage that sensitivity increases in comparison to base composition. The data on ballistic properties revealed that there is ca. 53 % increase in burning rate, while decrease in “n” value from 0.39 to 0.2 was obtained compared to base composition.