新型二茂铁基茚基茂配体的设计合成与电化学性能研究

发布时间：2018-06-03 06:35

本文选题：二茂铁茚基衍生物 + 取代联二茂铁茚衍生物　；参考：《内蒙古工业大学》2017年硕士论文

【摘要】：茚C_9H_8属苯并环戊二烯类化合物,可形成与环戊二烯基等电子的六电子茂配体,与许多过渡金属形成茂合物。同时,茚基的苯环也可与金属配位,形成半夹心配合物或夹心茂合物。因此,茚基衍生物具有多种配位形式,是构建金属配合物和茂合物的重要配体。自1951年二茂铁问世以来,受其独特夹心结构和氧化还原性质吸引,人们对二茂铁衍生物的研究热情始终未减。二茂铁茚基衍生物结合了二者的优点,以此为基础设计合成的新型茚基茂合物,预计在光电性能方面具有更加诱人的应用前景。在课题组前期工作的基础之上,本论文设计合成了一系列新型二茂铁基茚基衍生物,并研究了这些茂配体的电化学性质。本文工作为进一步设计合成具有光电功能的金属茂合物和配合物奠定了物质基础。论文主要工作如下:一、反应原料的制备1、依据文献方法,以二茂铁和正丁基锂为原料,N,N,N,N-四甲基乙二胺为保护剂,在室温下搅拌反应过夜,得到中间产物锂代二茂铁与四甲基乙二胺的络合物。将反应瓶降温至-78℃,然后加入单质碘自然升至室温继续反应2h,得到产物1,1’-二碘二茂铁I-C_5H_4Fe C_5H_4-I和副产物1,1’’-二碘联二茂铁I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-I。2、依据文献方法,以三甲基硅乙炔和2-溴茚为原料,双三苯基膦二氯化钯和碘化亚铜为催化剂,三乙胺为溶剂,在50℃加热回流8h,得到茚偶联产物三甲基硅基乙炔茚Ind-C≡CSi Me_3(Ind=2-C_9H_7,Me=CH_3)。以无水碳酸钾为碱助剂,甲醇为溶剂,在室温下将茚炔化合物Ind-C≡CSi Me_3水解,得到2-乙炔茚Ind-C≡CH。二、新型二茂铁基茚配体的设计合成1、采用Sonogashira偶联反应,以1,1’-二碘二茂铁I-C_5H_4Fe C_5H_4-I和2-乙炔茚Ind-C≡CH为原料,双三苯基膦二氯化钯和乙酸铜单水合物为催化剂,二异丙胺为溶剂,在86℃加热回流4h,合成了新型二茂铁茚基茂配体I-C_5H_4Fe C_5H_4-C≡C-Ind(1)和Ind-C≡C-C_5H_4Fe C_5H_4-C≡C-Ind(2)。2、采用Sonogashira偶联反应,在同样反应条件下,以1,1’-二碘联二茂铁I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-I和2-乙炔茚Ind-C≡CH为原料,合成了新型二茂铁茚基茂配体I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-C≡C-Ind(3),Ind-C≡C-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-C≡C-Ind(4)。3、采用Sonogashira偶联反应,以I-C_5H_4Fe C_5H_4-C≡C-Ind(1)和二茂铁乙炔Fc-C≡CH(Fc=C_5H_5Fe C_5H_4)为原料,双三苯基膦二氯化钯和乙酸铜单水合物为催化剂,二异丙胺为溶剂,在86℃加热回流4h,合成了新型二茂铁茚基茂配体Fc-C≡C-C_5H_4Fe C_5H_4-C≡C-Ind(5)。4、采用Sonogashira偶联反应,在同样反应条件下,以I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-C≡C-Ind(3)和二茂铁乙炔Fc-C≡CH为原料,得到新型二茂铁茚基茂配体HC≡C-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-C≡C-Ind(6)、Fc-C≡C-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-C≡C-Ind(7)和自偶产物Fc-C≡C-C≡C-Fc。三、制备茚基铁茂合物的尝试以I-C_5H_4Fe C_5H_4-C≡C-Ind(0.5 mmol)为原料,四氢呋喃THF为溶剂(10 m L),在-80℃下加入正丁基锂(0.5 mmol),低温搅拌反应15 min,自然升温至室温(5 h)。在室温下,向反应瓶中加入无水氯化亚铁(0.25 mmol),室温下搅拌反应16 h,停止反应。将反应产物分离纯化后没有得到预想的铁茂合物,却意外地得到一个新的茂配体Fc-C≡C-(3-C_4H_9)Ind(8)和一个已知化合物Fc-C≡C-Ind。四、新化合物1-8的电化学性能利用循环伏安(CV)法对八个新的二茂铁基茚基茂配体1-8的电化学性质进行了研究。结果表明,化合物1、2和8中对称和不对称的引入共轭的取代基团后,单二茂铁基茚衍生物的氧化电位值升高,变得更难氧化;与联二茂铁相比,联二茂铁衍生物3和4的两个取代基对二茂铁基之间电子交互作用基本没有影响;不对称地引入乙炔基和乙炔茚取代基团后,化合物6的两个二茂铁之间的电子交互作用明显减弱;炔基桥联的取代二茂铁茚基衍生物5,两个二茂铁基通过乙炔桥相连接,受金属-金属间距离的影响,两个二茂铁基之间的电子交互作用也减弱。在含三个二茂铁基茚衍生物7中,乙炔桥相连的两个二茂铁之间的电子交互作用?E_(21)(V)小于直接相连的二茂铁之间的电子交互作用?E_(32)(V)值。
[Abstract]:The Nene C_9H_8 is a benzo cyclopentadiene, which forms the six electron ligands with the cyclopentadienyl group and forms a compound with many transition metals. At the same time, the benzene ring of the Nene can also coordinate with the metal to form a semi sandwich or sandwich compound. Therefore, the derivatives of the Nene have a variety of coordination forms and are the construction of metal complexes and Since the advent of ferrocene, since the advent of two ferrocene in 1951, it has been attracted by its unique sandwich structure and redox properties. The enthusiasm for the study of two ferrocene derivatives has never been reduced. Two ferrocene derivatives combined with the advantages of the two, based on the design and synthesis of a new new Nene - based compound, which is expected to be in the optoelectronic properties. In this paper, a series of new two ferrocenyl derivatives are designed and synthesized in this paper, and the electrochemical properties of these ligands are studied. This work provides a material basis for the further design and synthesis of optoelectronic metallocene complexes and complexes. The work is as follows: first, the preparation of the reaction raw material 1, according to the literature method, using two ferrocene and n-butyl lithium as raw material, N, N, N, N- four methyl ethylenediamine as protective agent, stirring at room temperature for the night, get the complex of the intermediate product lithium two ferrocene and tetramethyldiamine. The reaction bottle is cooled to -78, and then adding the iodine to the room and naturally to the room. The temperature continued to react to 2h, the product 1,1 '- two iodine two ferrocene I-C_5H_4Fe C_5H_4-I and the by-product 1,1' - two iodide I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-I.2. According to the literature method, three methyl silicon acetylene and 2- bromide were used as raw materials, double three phenylphosphine two palladium chloride and copper iodide as catalyst, three ethylamine as solvent, and heated at 50. Refluxing 8h, three methylsilyl acetylene Ind-C CSi Me_3 (Ind=2-C_9H_7, Me=CH_3) was obtained. With anhydrous potassium carbonate as the alkali auxiliary, methanol as the solvent, the hydranyne compound Ind-C CSi Me_3 was hydrolyzed at room temperature, 2- acetylene Ind-C CH. two was obtained, and the new two ferrocene nynene ligand was designed and synthesized 1. The coupling reaction was used. Using 1,1 '- two iodide two ferrocene I-C_5H_4Fe C_5H_4-I and 2- acetylene Ind-C Ind-C CH as raw material, double three phenyl phosphine two palladium chloride and copper acetate monohydrate as catalyst, two isopropyl amine as solvent, refluxing 4H at 86 centigrade, synthesized a new type of Ferrocene and inhydrate ligand I-C_5H_4Fe C_5H_4-C C-Ind (1) and Ind-C C-C_5H_4Fe (2) Under the same reaction conditions, a new type of new two ferrocene, I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-I, I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-I and 2- acetylene Ind-C CH were synthesized under the same reaction conditions, and the new two ferrocene, the I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-C C-Ind (3) was synthesized. With Sonogashira coupling reaction, I-C_5H_4Fe C_5H_4-C C-Ind (1) and ferrocene acetylene Fc-C CH (Fc=C_5H_5Fe C_5H_4) as raw materials, double three phenyl phosphine two palladium chloride and copper acetate monohydrate as catalyst, two isopropyl amine as solvent and reflux 4H at 86 C, a new type of Ferrocene and inhydrate ligand Fc-C, C-C_5H_4Fe C_5H_4-C (5).4, using Sonogashira coupling reaction, under the same reaction conditions, using I-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-C C-Ind (3) and two ferrocene acetylene Fc-C CH as raw materials, the new type two ferrocenene ligene ligand HC C-C_5H_4Fe C_5H_4-C_5H_4Fe C_5H_4-C (7) and self couple (6) are obtained. The production of Fc-C C-C C-Fc. three, the preparation of the inhydrated iron llocene was made of I-C_5H_4Fe C_5H_4-C C-Ind (0.5 mmol) as raw material, tetrahydrofuran THF as a solvent (10 m L), adding n-butyl lithium (0.5 mmol) at -80 C, stirring at low temperature 15, naturally to room temperature (5). At room temperature, adding anhydrous ferrous chloride (0.25) into the reaction bottle at room temperature (0.25) A new ferrocene Fc-C C- (3-C_4H_9) Ind (3-C_4H_9) Ind (8) and a known compound, Fc-C C-Ind. four, and the electrochemical properties of the new compound 1-8 were obtained by the cyclic voltammetry (CV) method for eight new two ferrocenyl groups at room temperature. The electrochemical properties of the ligands 1-8 were studied. The results showed that the oxidation potential value of the mono ferrocene derivatives increased and became more difficult to oxidize after the conjugated and asymmetric substitutions were introduced in the compounds 1,2 and 8, and two substituents of the couplet ferrocene derivatives 3 and 4 were substituted for the electrons between the ferrocenyl group compared with the two ferrocene. After the asymmetric introduction of acetylene and acetylene substituent groups, the electronic interaction between the two two ferrocenes of the compound 6 significantly weakened; the substituent of the alkynyl bridged two ferrocene derivatives 5, two two Mao Tieji connected through the acetylene bridge, influenced by the metal to metal distance, and two two ferrocenyl groups. The electronic interaction between the three two ferrocene derivatives 7, the electronic interaction between the two two ferrocenic ferrocene connected by the acetylene bridge, E_ (21) (V) is less than the electronic interaction between the directly connected two ferrocene, E_ (32) (V).
【学位授予单位】：内蒙古工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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