本文選題：含銅配合物 + 異相催化��； 參考：《山西師范大學(xué)》2016年碩士論文

【摘要】：近年來,在綠色化學(xué)理念的倡導(dǎo)下,尋求高效、簡潔、廉價、綠色環(huán)保的有機(jī)合成方略受到化學(xué)家廣泛的關(guān)注。過渡金屬配合物的合成及其催化性能的研究已成為熱點(diǎn)。本論文旨在研究含銅配合物在C-C鍵構(gòu)筑反應(yīng)中的催化性能,探討反應(yīng)條件對其催化性能的影響,進(jìn)一步研究催化劑結(jié)構(gòu)與其催化活性的關(guān)系,以期對今后的工作提供理論指導(dǎo)。論文的主要工作分為四部分:第一章簡要介紹了含銅配合物的研究進(jìn)展,并對本課題的選題意義及本研究所取得的進(jìn)展進(jìn)行了描述。第二章以1,3,5-苯三四唑與醋酸銅為原料,通過溶劑熱方法構(gòu)筑方鈉石結(jié)構(gòu)的含銅金屬有機(jī)骨架材料[(Cu_4O_(0.27)Cl_(0.73)_3(H_(0.5)BTT)_8(H_2O)_(12)]·3MeOH·9DMF(1)。在配合物1結(jié)構(gòu)中,存在以氧/氯為中心的平面正方形[Cu_4O]/[Cu_4Cl]單元,通過與BTT~(3-)配體相連接形成具有陰離子性、孔隙性的三維(3,8-鏈接的)方鈉石的網(wǎng)絡(luò)結(jié)構(gòu)。與同構(gòu)的M-BTT MOFs相比較,在Cu_4簇內(nèi)μ_4-Cl被μ_4-O局部取代,有效地增強(qiáng)了金屬中心的路易斯酸性,同時避免了大體積客體[M(DMF)6]2+陽離子對MOF孔道的占據(jù),有效擴(kuò)充孔道體積。配合物1經(jīng)過脫水,形成具有不飽和配位Cu_2+中心的配合物1￠[(Cu_4O_(0.27)Cl_(0.73)_3(H_(0.5)BTT)_8]。以醛酮的氰硅化反應(yīng)為模型,對其作為路易斯酸的催化性能進(jìn)行探索。在1 mol%的催化劑用量下,成功地實(shí)現(xiàn)了異相催化的C-C鍵的構(gòu)筑,合成了一系列氰醇類化合物。該反應(yīng)無須任何堿及溶劑,且催化劑穩(wěn)定性良好。此外,與Mn-BTT相比,僅僅是其用量的十一分之一,即可使苯甲醛的轉(zhuǎn)化率高達(dá)96%。這一結(jié)果表明,我們成功地通過后合成修飾,增加了MOF 1的路易斯酸性,使Cu-BTT MOFs的催化活性得到顯著提高。第三章以鄰菲Up啉與硝酸銅為原料,構(gòu)筑了三配位的平面雙核銅配合物Cu_2(ophen)_2(2)和四核混合價的配合物[Cu_4(ophen)_4(tp)](3)。雙核Cu(I)配合物2中配體是以脫質(zhì)子的2-羥基-1,10-菲Up啉形式呈現(xiàn),這說明在反應(yīng)過程中伴隨著鄰菲Up啉的羥基化。基于已有文獻(xiàn)報道,我們推測其具有活化分子氧的潛能,并分別通過需氧的芳基硼酸的自身偶聯(lián)和格拉澤反應(yīng)來對其的催化活性進(jìn)行了研究。值得注意的是,在無毒無污染的綠色溶劑水為主要溶劑時,Cu_2(ophen)_2催化硼酸的自身偶聯(lián)體系主產(chǎn)物依然是聯(lián)苯而非酚類,這在以往的文獻(xiàn)報道中是很難實(shí)現(xiàn)的。在此基礎(chǔ)上,我們將這兩種配合物應(yīng)用于需氧的格拉澤反應(yīng),在綠色環(huán)保的水為溶劑、室溫、空氣/氧氣氛圍、無須任何堿,就可以成功地實(shí)現(xiàn)99%的高轉(zhuǎn)化率。值得一提的是,配合物3在常規(guī)溶劑中溶解性較差,使其在該反應(yīng)中以非均相的形式發(fā)揮作用,循環(huán)催化五次后,依然保持較高的催化活性。第四章對本論文的相關(guān)工作進(jìn)行了總結(jié),并對該課題的研究前景進(jìn)行展望。
[Abstract]:In recent years, based on the idea of green chemistry, the strategy of organic synthesis with high efficiency, simplicity, low cost and green environment has been paid more and more attention by chemists. The synthesis of transition metal complexes and their catalytic properties have become a hot topic. The purpose of this paper is to study the catalytic performance of copper-containing complexes in C-C bond building reactions, to explore the effect of reaction conditions on their catalytic performance, and to further study the relationship between the structure of the catalysts and their catalytic activity, in order to provide theoretical guidance for future work. The main work of this paper is divided into four parts: the first chapter briefly introduces the research progress of copper-containing complexes, and describes the significance of the topic and the progress of the research. In the second chapter, the copper-containing organometallic organic skeleton material with the structure of sodium oblate was constructed by solvothermal method using 1 / 3 triazole and copper acetate as raw materials. [3MeOH 9DMF _ 1] 3MeOH 9DMF _ (1). In the structure of complex 1, there are planar square [Cu_4O] / [Cu_4Cl] units centered on oxygen / chlorine, which form anion, porosity and three-dimensional (3 ~ (38) -linked) sodium montmorillonite network structure by joining with BT-T _ (3) ~ (3) ligands. Compared with the isomorphic M-BTT MOFs, 渭 _ 4-Cl in the Cu_4 cluster is partially replaced by 渭 _ 4-O, which effectively enhances the Lewis acidity of the metal center, avoids the occupation of large volume [M(DMF)6] _ 2 cations to the MOF channels, and effectively expands the pore volume. Complex 1 is dehydrated to form a complex with unsaturated coordination Cu_2 centers. The catalytic activity of aldehydes and ketones as Lewis acid was investigated by using the cyanosilication reaction of aldehydes and ketones as a model. A series of cyanide alcohols were synthesized by constructing heterogeneous C-C bonds at the amount of 1 mol% catalyst. There is no need for any alkali or solvent in the reaction, and the catalyst is stable. In addition, compared with Mn-BTT, the conversion rate of benzaldehyde was as high as 96% when the amount of benzaldehyde was only 1/11. The results show that the Lewis acidity of MOF 1 is increased and the catalytic activity of Cu-BTT MOFs is improved significantly through the post synthesis modification. In chapter 3, a tri-coordinated planar binuclear copper complex, Cu _ 2O _ 2 / T _ 2 / C _ 2 / T _ 2 / Cu _ 4P _ p _ 4 / T _ 3, was constructed from o-phenanthroline and copper nitrate as raw materials. The ligand in binuclear CuNI) complex 2 is in the form of deprotonated 2-hydroxyl -1-10-phenanthroline, which indicates that the hydroxylation of o-phenanthroline is accompanied by the reaction process. Based on the previous reports, we speculated that it has the potential of activating molecular oxygen, and studied its catalytic activity by self-coupling of aerobic aryl boric acid and Glazer reaction respectively. It is worth noting that the main product of the self-coupling system for the catalytic reaction of boric acid is still biphenyl rather than phenols when the non-toxic and pollution-free green solvent water is the main solvent. This is difficult to achieve in the previous literature. On this basis, we have applied these two complexes to aerobic Glazer reaction. The high conversion rate of 99% can be successfully achieved by using green water as solvent, room temperature, air / oxygen atmosphere and no alkali. It is worth mentioning that the solubility of complex 3 in conventional solvents is poor, so that complex 3 acts in heterogeneous form in this reaction. After five cycles of cyclic catalysis, complex 3 still maintains high catalytic activity. The fourth chapter summarizes the related work of this paper, and prospects for the research of this topic.
【學(xué)位授予單位】：山西師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.251

【參考文獻(xiàn)】

相關(guān)期刊論文 前3條

1 湯德祥;;一價銅配合物合成研究進(jìn)展[J];科技信息(科學(xué)教研);2008年23期

2 白麗娟;雷福厚;莫麗君;羅影;黃永忠;;歧化松香胺Schiff堿-銅配合物催化苯乙烯氧化反應(yīng)的研究[J];林產(chǎn)化學(xué)與工業(yè);2007年S1期

3 王榮民,王建人,郝成君,王云普;氨基酸希夫堿銅配合物的合成及催化烯烴氧化性能[J];西北師范大學(xué)學(xué)報(自然科學(xué)版);1999年04期

相關(guān)博士學(xué)位論文 前1條

1 劉定華;銅配合物催化劑制備及其羰基合成碳酸二甲酯性能的研究[D];南京理工大學(xué);2010年

，

本文編號：1801310