本文選題：氮雜環(huán)卡賓金屬配合物 + 手性單齒膦配體金屬配合物��； 參考：《華東師范大學(xué)》2017年碩士論文

【摘要】：氮雜環(huán)卡賓金屬配合物與手性膦配體金屬配合物是金屬有機(jī)催化領(lǐng)域中兩類非常重要的催化劑,已廣泛應(yīng)用于許多均相及不對稱反應(yīng)。在多相催化領(lǐng)域,多孔有機(jī)聚合物作為一種新型的載體已經(jīng)在許多反應(yīng)中展現(xiàn)了出色的穩(wěn)定性。本論文將氮雜環(huán)卡賓金屬配合物及手性膦配體金屬配合物與多孔有機(jī)聚合物結(jié)合起來,在保證金屬配合物催化活性的同時發(fā)揮多孔有機(jī)聚合物特性,實現(xiàn)催化劑的循環(huán)利用。具體工作如下:1)在傳統(tǒng)的氮雜環(huán)卡賓配體結(jié)構(gòu)中引入烯丙基官能團(tuán),并將得到的1,3-二-(2,6-二異丙基-4-烯丙基苯基)氯化咪唑5與不同的金屬活性物種配位制得相應(yīng)的烯丙基功能化的氮雜環(huán)卡賓金屬配合物6。進(jìn)一步將這些金屬配合物分別通過溶劑熱合成法與DVB發(fā)生自由基聚合形成多孔有機(jī)聚合物,成功地制備了三種含不同金屬(銅、銀、金)的多孔有機(jī)聚合物POP-NHC-Cu、POP-NHC-Ag、POP-NHC-Au。通過電感耦合等離子體原子發(fā)射光譜、氮氣等溫吸脫附、掃描電鏡、透射電鏡、熱重分析等測試技術(shù)對催化材料進(jìn)行了詳細(xì)的表征,證明了合成的多孔有機(jī)聚合物材料是一類具有較大比表面積和孔體積、良好的熱穩(wěn)定性的無定形多孔材料,且金屬含量可調(diào)。將POP-NHC-Cu系列催化劑應(yīng)用于多聚甲醛、苯乙炔和吡咯烷的三組分偶聯(lián)反應(yīng)以及水相中進(jìn)行的苯乙炔、疊氮化鈉和芐溴的三組分1,3-偶極環(huán)加成反應(yīng);POP-NHC-Ag系列催化劑應(yīng)用于醛、炔、胺的三組分偶聯(lián)反應(yīng);POP-NHC-Au系列催化劑應(yīng)用于二苯乙炔的水合反應(yīng),催化劑都表現(xiàn)出良好的催化性能,在每個催化體系中各個催化劑都能循環(huán)使用5次以上且催化活性基本保持不變。2)對(R)-N-[2-(二苯基膦)苯亞甲基]-2-甲基丙烷-2-亞磺酰胺8進(jìn)行苯乙烯基官能團(tuán)化修飾,然后將制得的(R)-N-(S)-[2-(二苯基膦)苯基-4-乙烯基苯基]甲基-2-甲基丙烷-2-亞磺酰胺9與DVB進(jìn)行自由基聚合反應(yīng)形成多孔有機(jī)聚合物負(fù)載的手性單齒膦配體POP-CMP。通過氮氣等溫吸脫附、掃描電鏡、透射電鏡、熱重分析等測試技術(shù)對其進(jìn)行了詳細(xì)的表征,證明POP-CMP是一種具有較大比表面積和孔體積、良好的熱穩(wěn)定性的無定形多孔材料。將POP-CMP進(jìn)一步與活性金屬進(jìn)行配位得到POP-CMP-AuNTf_2催化劑。以烯炔酮和硝酮的不對稱環(huán)加成反應(yīng)為模板反應(yīng),對POP-CMP-AuNTf_2催化劑進(jìn)行催化性能的探究,研究發(fā)現(xiàn)催.化劑在模板反應(yīng)中沒有催化效果。對催化劑失活原因進(jìn)行了初步的探究,從POP-CMP的固體核磁共振磷譜表征發(fā)現(xiàn),手性單齒膦配體在交聯(lián)聚合過程中被氧化,由此造成催化劑負(fù)載后失去活性。
[Abstract]:Chiral phosphine ligand metal complexes are two important catalysts in the field of organometallic catalysis and have been widely used in many homogeneous and asymmetric reactions. In the field of heterogeneous catalysis, porous organic polymers as a new carrier have shown excellent stability in many reactions. In this paper, the metal complexes of nitrogen heterocyclic carbene and chiral phosphine ligands are combined with porous organic polymers to ensure the catalytic activity of the metal complexes and to realize the recycling of the catalysts. The specific work is as follows: (1) introduction of allyl functional groups into the traditional carbene ligands of heterocyclic nitrogen, The anallyl functionalized carbene metal complex 6 was synthesized by the coordination of 1'3'3'2'2'6'- diisopropyl-4-allyl phenyl) imidazolium chloride with different metal active species. These metal complexes were further polymerized with DVB by solvothermal synthesis to form porous organic polymers. Three kinds of POP-NHC-Cu POP-NHC-AgPOP-NHC-Au-containing different metals (copper, silver and gold) were successfully prepared. The catalytic materials were characterized by inductively coupled plasma atomic emission spectrometry, isothermal adsorption and desorption of nitrogen, scanning electron microscope, transmission electron microscope and thermogravimetric analysis. It is proved that the synthesized porous organic polymer is a kind of amorphous porous material with large specific surface area and pore volume and good thermal stability, and the metal content is adjustable. The POP-NHC-Cu series of catalysts were applied to the three-component coupling reactions of polyformaldehyde, phenylacetylene and pyrrolidine, as well as the three components of phenylacetylene, sodium azide and benzyl bromide in aqueous phase. The POP-NHC-Ag series catalysts were applied to aldehyde, acetylene, benzyl bromide, sodium azide and benzyl bromide. POP-NHC-Au series of catalysts for the hydration of diphenylacetylene show good catalytic performance. In each system, each catalyst can be reused for more than five times, and the catalytic activity remains basically unchanged. 2) the styrene group modification of RN- [2-( diphenylphosphine) phenylmethylene] -2-methylpropane-2-sulfonamide 8 is carried out. The chiral monodentate phosphine ligands POP-CMP supported by porous organic polymer were synthesized by the free radical polymerization of the DVB with the prepared RN- N-N- (S-)-[2-( diphenylphosphine) phenyl -4vinylphenyl] methyl -2-methylpropane-2-sulfonamide (DVB). The isothermal adsorption and desorption of nitrogen, scanning electron microscope, transmission electron microscope and thermogravimetric analysis were used to characterize POP-CMP in detail. It is proved that POP-CMP is an amorphous porous material with large specific surface area and pore volume and good thermal stability. POP-CMP was further coordinated with active metal to obtain POP-CMP-AuNTf_2 catalyst. The asymmetric cycloaddition reaction of alkylethynone and nitrone was used as a template to investigate the catalytic performance of POP-CMP-AuNTf_2 catalyst. The catalyst has no catalytic effect in the template reaction. The reason for the deactivation of the catalyst was studied. It was found that the chiral monodentate phosphine ligands were oxidized during the crosslinking polymerization from the solid state NMR phosphorus spectra of POP-CMP, which resulted in the loss of activity after the catalyst was loaded.
【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4
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本文編號：1883960