二茂铁基取代吡啶、嘧啶和三嗪类化合物的合成及电化学性能研究

发布时间：2018-05-23 22:08

  本文选题：二茂铁 + 六元芳环　； 参考：《内蒙古工业大学》2017年硕士论文

【摘要】：由于二茂铁衍生物在电化学领域表现出良好的氧化还原特性,很多研究者在二茂铁功能化分子的构建和电化学性质研究方面进行了探索,特别是在二茂铁单元间电荷传递通道和影响因素等方面开展了大量工作,并且总结出二茂铁单元间的电子交互主要受桥的类型、桥原子种类、氧化还原中心的空间距离、取代基诱导效应、桥电荷密度、分子拓扑结构以及支持电解质种类等因素的影响。在前期关于二茂铁模型化合物电子传递性能研究当中,人们在各种原子桥、共轭和非共轭线型桥、共轭五元杂环桥以及苯基桥联的二茂铁化合物进行了大量的研究工作,而对于以六元杂环为桥的多二茂铁化合物电化学传递特性的研究报道甚少。本文采用Negishi偶联反应成功合成了六种二茂铁基取代吡啶、嘧啶和三嗪化合物,并结合结构、紫外光谱、理论计算对其循环伏安性质进行了研究。1、二茂铁基取代吡啶、嘧啶和三嗪的合成论文采用新制备的二茂铁基氯化锌,在[1,1'-双(二苯基膦基)二茂铁]二氯化钯[Pd(dppf)Cl2]催化下,分别与不同当量的2,4,6-三溴吡啶、2,4,6-三氯-1,3-嘧啶、2,4,6-三氯-1,3,5-三嗪发生Negishi偶联反应,合成了三种二茂铁基取代吡啶、嘧啶和三嗪化合物:2-溴-4,6-双二茂铁基吡啶(1)、2-氯-4,6-双二茂铁基-1,3-嘧啶(2)、2-氯-4,6-双二茂铁基-1,3,5-三嗪(3);三种三二茂铁基取代吡啶、嘧啶和三嗪化合物:2,4,6-三二茂铁基吡啶(4)、2,4,6-三二茂铁基-1,3-嘧啶(5)、2,4,6-三二茂铁基-1,3,5-三嗪(6)。论文采用元素分析、红外光谱、质谱、核磁共振、紫外光谱等对化合物的组成和结构进行了表征,并通过X-射线单晶衍射确定了化合物3、4、6的分子与晶体结构。化合物1、2、3、5为首次合成的4个新化合物;化合物3和6为首次报道的新型分子晶体结构。2、电化学性质研究论文采用循环伏安法对六种化合物进行了电化学测试,同时结合理论计算、晶体结构对化合物中二茂铁单元间电子交互通道和影响电子交互的因素进行了分析。研究结果表明:双二茂铁基吡啶、嘧啶、三嗪三个化合物中二茂铁单元间的电荷传递不是通过最短的桥,而是通过π共轭桥而发生作用的,同时随着π共轭桥的电荷密度减小,二茂铁单元间的电子交互作用逐渐减小,并且随着中心环氮原子数的增多,体系的共轭性逐渐增强,导致对二茂铁单元电荷的分散作用加大,使得首个氧化峰电位向高电位偏移;三二茂铁基吡啶、嘧啶、三嗪三个化合物中二茂铁单元的电子交互作用也是随着π共轭桥的电荷密度减小而逐渐减小的,同时三者的第一氧化峰电位随着HOMO轨道能量的降低而依次升高。
[Abstract]:Because ferrocene derivatives exhibit good redox properties in the electrochemical field, many researchers have explored the construction of ferrocene functionalized molecules and the study of electrochemical properties. In particular, a great deal of work has been done in charge transfer channels and influencing factors among ferrocene units, and it is concluded that the electronic interaction between ferrocene units is mainly affected by the type of bridge, the type of bridge atoms, the space distance of redox centers, and so on. The effects of substituent inductive effect, bridge charge density, molecular topological structure and kinds of supporting electrolytes. In previous studies on the electron transport properties of ferrocene model compounds, a great deal of work has been done on various atomic bridges, conjugated and unconjugated linear bridges, conjugated five-element heterocyclic bridges and phenyl bridged ferrocene compounds. However, there are few reports on the electrochemical transport properties of polyferrocene compounds with hexahedral heterocycles as the bridge. In this paper, six ferrocenyl substituted pyridine, pyrimidine and triazine compounds were successfully synthesized by Negishi coupling reaction. The synthesis of pyrimidine and triazine was studied by using newly prepared ferrocenyl zinc chloride under the catalysis of [1 (1) -bis (diphenylphosphine) ferrocene] palladium [Pd(dppf)Cl2]. Three kinds of ferrocenyl substituted pyridine were synthesized by Negishi coupling reaction with different equivalent 2H 4N 6- trichloropyridine-6-trichloro-6-trichloro-3-pyrimidine, respectively, in which three ferrocenyl pyridine substituted pyridines were synthesized. Pyrimidine and triazine compounds: 2-bromo-6-diferrocenylpyridine, 2-chloro-4-diferrocenyl, 6-diferrocenyl, 2-pyrimidine, 2-chloro-4-diferrocenyl, 6-diferrocenyl, 5-triazinone; three kinds of ferrocenyl substituted pyridine, Pyrimidine and triazine compounds 2: 4, 4, 6-triferrocenyl pyridine, 2, 2, 6-triferrocenyl-1, 1, 3-pyrimidine, 2, 4, 6-triferrocenyl, 3-1, 3-triazinyl, 6-triferrocenyl, 5-triazinyl, 6-triferrocenyl, 6-triferrocenylpyridine. The composition and structure of the compound were characterized by elemental analysis, IR, MS, NMR and UV spectra, and the molecular and crystal structure of compound 3O4N6 was determined by X-ray single crystal diffraction. Compounds 1, 2, O, 3 and 5 are four new compounds synthesized for the first time, and compounds 3 and 6 are new molecular crystal structures reported for the first time. The electrochemical properties of these compounds have been measured by cyclic voltammetry. At the same time, the crystal structure was used to analyze the electronic interaction channel between ferrocene units and the factors affecting the electronic interaction. The results show that the charge transfer between ferrocene units in three compounds, pyridine, pyrimidine and triazine, occurs not by the shortest bridge, but by 蟺 conjugate bridge, and decreases with the decrease of the charge density of 蟺 conjugate bridge. The electron interaction between ferrocene units decreases gradually, and with the increase of the number of central ring nitrogen atoms, the conjugation of the system increases gradually, which leads to the dispersion of the charge of ferrocene units. The electron interaction of ferrocene units in ferrocene pyridine, pyrimidine and triazine compounds decreases with the decrease of the charge density of 蟺 conjugate bridge. At the same time, the first oxidation peak potential of the three increases with the decrease of HOMO orbital energy.
【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】：O627.81

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中国期刊全文数据库 前1条

1 刘万毅,袁耀锋,张凌云,王积涛;烷基桥联双二茂铁衍生物的取代基效应与电化学性质的研究[J];高等学校化学学报;1998年08期

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