取代的四甲基环戊二烯基铼羰基配合物的合成及其催化傅—克氏烷基化反应研究
发布时间：2018-06-26 22:26
本文选题：环戊二烯基 + 铼羰基配合物 ； 参考：《河北师范大学》2017年硕士论文
【摘要】：由于环戊二烯基配体可与过渡金属形成较牢固的化学键及其结构较易修饰等特点,被广泛用于多种多样具有不同结构和性能的金属有机配合物的合成,因此含环戊二烯基配体的过渡金属有机化合物在金属有机化学中占有非常重要的地位,在催化(烯烃的聚合、偶联反应、酮的氢化、醇的氧化等)和构建分子材料上具有很高的应用价值,一直受到化学工作者的广泛关注。本文设计合成了11种烃基或芳烃取代的四甲基环戊二烯基金属铼羰基配合物,考察了烃基和芳烃取代基对配合物结构的影响,并研究了这些配合物在苯衍生物Friedel-Crafts烷基化反应中的催化活性。具体内容如下:首先,烃基或芳基取代的四甲基环戊二烯配体分别与Re2(CO)10在二甲苯中回流反应,分离得到了6个烃基取代的四甲基环戊二烯基铼羰基配合物[(η5-C_5Me_4R)Re(CO)_3](R=allyl(7),~iPr(8),~nBu(9),~tBu(10),~Bz(11),CH(CH2)4(12))和5个芳基取代的四甲基环戊二烯基铼羰基配合物[(η5-C_5Me_4R)Re(CO)_3](R=Ph(18),4-CH3Ph(19),4-OCH_3Ph(20),4-ClPh(21),4-BrPh(22)),用IR、1H NMR、13C NMR和元素分析对其进行了表征,并用X-射线单晶衍射法测定了它们的晶体结构。它们都属于三条腿的钢琴凳式结构,均为单核配合物,铼原子与环戊二烯基环以η5模式配位,铼原子连有三个端羰基。其次,研究了这11种配合物在苯衍生物Friedel-Crafts烷基化反应的催化活性,结果表明:11个配合物均有催化活性,茂环上的取代基对配合物的催化活性有一定的影响;与传统催化剂相比,催化用量少。
[Abstract]:Cyclopentadienyl ligands are widely used in the synthesis of organometallic complexes with different structures and properties due to their strong chemical bonds with transition metals and their easy modification. Therefore, transition metal organic compounds containing cyclopentadienyl ligands play a very important role in organometallic chemistry, and play an important role in catalysis (polymerization of olefins, coupling reaction, hydrogenation of ketones. The oxidation of alcohols and the construction of molecular materials have high application value and have been widely concerned by chemical workers. Eleven alkyl or aromatics substituted tetramethylcyclopentadienyl metal rhenium carbonyl complexes were designed and synthesized. The effects of hydrocarbon and aromatic substituents on the structure of the complexes were investigated. The catalytic activity of these complexes in Friedel-Crafts alkylation of benzene derivatives was studied. The main contents are as follows: firstly, the refluxing reaction of alkyl or aryl substituted tetramethyl cyclopentadiene ligands with Re2 (CO) 10 in xylene, 鍒嗙寰楀埌浜，
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