多孔有机聚合物负载的氮杂环卡宾金属配合物及手性单齿膦配体金属配合物的制备和应用

发布时间：2018-05-13 16:32

  本文选题：氮杂环卡宾金属配合物 + 手性单齿膦配体金属配合物　； 参考：《华东师范大学》2017年硕士论文

【摘要】：氮杂环卡宾金属配合物与手性膦配体金属配合物是金属有机催化领域中两类非常重要的催化剂,已广泛应用于许多均相及不对称反应。在多相催化领域,多孔有机聚合物作为一种新型的载体已经在许多反应中展现了出色的稳定性。本论文将氮杂环卡宾金属配合物及手性膦配体金属配合物与多孔有机聚合物结合起来,在保证金属配合物催化活性的同时发挥多孔有机聚合物特性,实现催化剂的循环利用。具体工作如下:1)在传统的氮杂环卡宾配体结构中引入烯丙基官能团,并将得到的1,3-二-(2,6-二异丙基-4-烯丙基苯基)氯化咪唑5与不同的金属活性物种配位制得相应的烯丙基功能化的氮杂环卡宾金属配合物6。进一步将这些金属配合物分别通过溶剂热合成法与DVB发生自由基聚合形成多孔有机聚合物,成功地制备了三种含不同金属(铜、银、金)的多孔有机聚合物POP-NHC-Cu、POP-NHC-Ag、POP-NHC-Au。通过电感耦合等离子体原子发射光谱、氮气等温吸脱附、扫描电镜、透射电镜、热重分析等测试技术对催化材料进行了详细的表征,证明了合成的多孔有机聚合物材料是一类具有较大比表面积和孔体积、良好的热稳定性的无定形多孔材料,且金属含量可调。将POP-NHC-Cu系列催化剂应用于多聚甲醛、苯乙炔和吡咯烷的三组分偶联反应以及水相中进行的苯乙炔、叠氮化钠和苄溴的三组分1,3-偶极环加成反应;POP-NHC-Ag系列催化剂应用于醛、炔、胺的三组分偶联反应;POP-NHC-Au系列催化剂应用于二苯乙炔的水合反应,催化剂都表现出良好的催化性能,在每个催化体系中各个催化剂都能循环使用5次以上且催化活性基本保持不变。2)对(R)-N-[2-(二苯基膦)苯亚甲基]-2-甲基丙烷-2-亚磺酰胺8进行苯乙烯基官能团化修饰,然后将制得的(R)-N-(S)-[2-(二苯基膦)苯基-4-乙烯基苯基]甲基-2-甲基丙烷-2-亚磺酰胺9与DVB进行自由基聚合反应形成多孔有机聚合物负载的手性单齿膦配体POP-CMP。通过氮气等温吸脱附、扫描电镜、透射电镜、热重分析等测试技术对其进行了详细的表征,证明POP-CMP是一种具有较大比表面积和孔体积、良好的热稳定性的无定形多孔材料。将POP-CMP进一步与活性金属进行配位得到POP-CMP-AuNTf_2催化剂。以烯炔酮和硝酮的不对称环加成反应为模板反应,对POP-CMP-AuNTf_2催化剂进行催化性能的探究,研究发现催.化剂在模板反应中没有催化效果。对催化剂失活原因进行了初步的探究,从POP-CMP的固体核磁共振磷谱表征发现,手性单齿膦配体在交联聚合过程中被氧化,由此造成催化剂负载后失去活性。
[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.
【学位授予单位】：华东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
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本文编号：1883960