【作者】 王辉；

【导师】 盛鸿婷；

【作者基本信息】 安徽大学 ， 有机化学， 2013， 硕士

【摘要】 催化剂的催化活性主要取决于中心金属及其所在的配位环境。钙金属廉价易得、具有很好的生物相容性,近年来在催化领域中备受人们关注。倍半硅氧烷(POSS)具有很好的配位能力,且具有很好的修饰组装性能,是一类新型大分子高聚物配体。本文在调研大量文献的基础上,综述了环戊二烯基、烷(芳)氧基配体、p-二酮亚胺类配体等的钙金属配合物、路易斯酸以及计算化学的研究进展基应用,提出本论文的设计思想。1、本文借助倍半硅氧烷L1=(Bu)7Si7O9(OH)3合成了两类席夫碱基配体,L2=(1Bu)7Si8O12-(CH2)3-N=C-Ar-OH; L3=(1Bu)7Si8O12-(CH2)3-N=C-Ar(1Bu)2(OH)通过红外光谱、核磁共振氢谱、元素分析表征。2、将L1、L2及L3与金属钠反应得到相应的钠盐,然后再和碘化钙反应得到相应的钙配合物。L1-Ca、L2-Ca、L3-Ca均通过核磁共振氢谱、红外光谱、元素分析、钙含量分析确定了它们的组成及结构。3、以2-吡啶甲醇(L4)、N,N-二甲基乙醇胺(L5)、异丙醇为配体(L6),高效合成了三种含碱金属的烷氧基杂多核金属簇合物L4-Ca={Ca2(OCH2-Py)gNa4(THF)2.5}、 L5-Ca={Ca2(OCH2CH2NMe2)8Na4(THF)2.5}、 L6-Yb={Yb4O4(O1Pr)16Na12｝,并对它们进行了核磁共振氢谱、红外光谱、元素分析、钙及钠含量分析确定了其分子组成。同时对L6-Yb进行了X单晶衍射、计算化学理论计算,确定该簇合物的结构。4、系统研究了烷氧基钙金属配合物对胍化反应、Tishchenko反应的催化活性,发现簇合物L4-Ca对胍化反应、Tishchenko反应均有较高的催化活性。5、研究了路易斯酸体系催化氧化2,6-二叔丁基苯酚(DBP)成对苯醌(TBDPQ)的反应,发现FeCl3在催化醌合成中有较高的催化活性,而且催化剂可以循环使用五次以上。更多还原

【Abstract】 The performance of catalyze mainly depends on the central metal and the coordination environment of the central metal. Cheap calcium metal has good biocompatibility, the use of calcium metal as a catalyst cause for concern recently. The polyhedral silsequioxanes (POSS) have effective coordination property and can be modified to generate kinds of new polyhedral silsequioxanes easily. We give a summarize of calcium complex which involve cyclopentadienyl calcium, alkoxide calcium,β-diiminato calcium and the application in the synthesis of guanidine and Tishchenko reaction after survey the kinds of literatures in this thesis. Besides, we sum up the application of Lewis Acids system, the computionl chemistry in organometallic chemistry briefly and progose the ideas of this thesis.1.Two types of alkoxide salen ligands (L2, L3) were synthesized through the simple synthetic method with the alkoxide ligand raw material polyhedral silsequioxanes{Ll=(Bu)7Si7O9(OH)3}:L2=(Bu)7Si8O12-(CH2)3-N=C-Ph-OH, L3=(iBu)7Si8O12-(CH2)3-N=C-Ph(1Bu)2(OH). Complexs were characterized by IR spectroscopy,1H NMR spectroscopy and elemental analysis.2. L1, L2and L3with the metal sodium reaction of the corresponding sodium salt, and then exchange of the corresponding calcium iodide, calcium complexes. And all of them (L1-Ca, L2-Ca and L3-Ca) were characterized by IR spectroscopy,1H NMR spectroscopy and elemental analysis, and we have given the structures of all.3. Three negative alkaline clusters L4-Ca={Ca2(OCH2-Py)8Na4(THF)2.5}, L5-Ca={Ca2(OCH2CH2NMe2)8Na4(THF)2.5}, L6-Yb={Yb4O4(O1Pr),6Na12} were synthesized by the alkaline ligands L4=2-Pyridinemethanol, L5=N,N-dimethyl ethanolamine, L6=isopropyl alcohol. And all of them (L4-Ca, L5-Ca and L6-Yb) were characterized by IR spectroscopy,1H NMR spectroscopy and elemental analysis the metal content to determine their compositions and structures. X-ray diffraction and ancillary computational analysis of the optimized molecular unit was provided to determine the structure of L6-Yb.4. The factors affecting the activity of alkali metal complexes of the catalytic reaction of guanidine and Tishchenko was studied by alkaline calcium complexes, the cluster L4-Ca={Ca2(OCH2CH2NMe2)8Na4(THF)2.5} shows a high catalytic activity than other catalysts.5. An efficient and simple method for the preparation of3,3’,5,5’-tetra-tert-butyl-4,4’-diphenoquinone (TBDPQ) is reported using Lewis Acid as an effective catalyst in the presence of molecular oxygen from2,6-di-tert-butylphenol (DBP). The oxidation reaction was found to proceed in two steps and the oxidation kinetics for FeCl3system was examined in detail. Results illustrated that FeCl3was the most effective and reusable catalyst, it can be reused five times.更多还原