本文選題：環(huán)戊二烯基 + 錸羰基配合物��； 參考：《河北師范大學(xué)》2017年碩士論文

【摘要】：由于環(huán)戊二烯基配體可與過(guò)渡金屬形成較牢固的化學(xué)鍵及其結(jié)構(gòu)較易修飾等特點(diǎn),被廣泛用于多種多樣具有不同結(jié)構(gòu)和性能的金屬有機(jī)配合物的合成,因此含環(huán)戊二烯基配體的過(guò)渡金屬有機(jī)化合物在金屬有機(jī)化學(xué)中占有非常重要的地位,在催化(烯烴的聚合、偶聯(lián)反應(yīng)、酮的氫化、醇的氧化等)和構(gòu)建分子材料上具有很高的應(yīng)用價(jià)值,一直受到化學(xué)工作者的廣泛關(guān)注。本文設(shè)計(jì)合成了11種烴基或芳烴取代的四甲基環(huán)戊二烯基金屬錸羰基配合物,考察了烴基和芳烴取代基對(duì)配合物結(jié)構(gòu)的影響,并研究了這些配合物在苯衍生物Friedel-Crafts烷基化反應(yīng)中的催化活性。具體內(nèi)容如下:首先,烴基或芳基取代的四甲基環(huán)戊二烯配體分別與Re2(CO)10在二甲苯中回流反應(yīng),分離得到了6個(gè)烴基取代的四甲基環(huán)戊二烯基錸羰基配合物[(η5-C_5Me_4R)Re(CO)_3](R=allyl(7),~iPr(8),~nBu(9),~tBu(10),~Bz(11),CH(CH2)4(12))和5個(gè)芳基取代的四甲基環(huán)戊二烯基錸羰基配合物[(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和元素分析對(duì)其進(jìn)行了表征,并用X-射線單晶衍射法測(cè)定了它們的晶體結(jié)構(gòu)。它們都屬于三條腿的鋼琴凳式結(jié)構(gòu),均為單核配合物,錸原子與環(huán)戊二烯基環(huán)以η5模式配位,錸原子連有三個(gè)端羰基。其次,研究了這11種配合物在苯衍生物Friedel-Crafts烷基化反應(yīng)的催化活性,結(jié)果表明:11個(gè)配合物均有催化活性,茂環(huán)上的取代基對(duì)配合物的催化活性有一定的影響;與傳統(tǒng)催化劑相比,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，

本文編號(hào)：2071626