本文選題：氮雜環(huán)卡賓 + 稀土配合物��； 參考：《浙江大學(xué)》2017年碩士論文

【摘要】：本文制備了一系列單酚取代的氮雜環(huán)卡賓類配體前體,并用核磁共振譜和元素分析方法表征了配位體前體的結(jié)構(gòu)。選取了其中兩種四氫嘧啶配體前體與六甲基硅胺基稀土化合物進(jìn)行配位反應(yīng),成功制備了四種結(jié)構(gòu)新穎的氮雜環(huán)卡賓胺基稀土配合物,并用單晶X-射線衍射分析、核磁共振譜表征了配合物的精確結(jié)構(gòu)。將所得配合物用于催化ε-已內(nèi)酯開環(huán)聚合,發(fā)現(xiàn)此類配合物無論是單組份體系或是與異丙醇組成雙組份體系,都能有效地催化ε-已內(nèi)酯開環(huán)聚合。通過萘酚取代的氮雜環(huán)卡賓配體前體3-((2-hydroxynaphthalenyl)methyl)-1-mesityl-3,4,5,6-tetrahydropyrimidinium chloride H2L1 與六甲基硅胺基稀土Ln[N(SiMe3)2]3反應(yīng),合成了含有卡賓-鉀結(jié)構(gòu)的胺基稀土配合物L(fēng)1KLnN”3(Ln=Y,1a;Nd,1b)。選取苯酚取代的氮雜環(huán)卡賓類配體前體3-(2-hydroxybenzyl)-1-mesityl-3,4,5,6-tetrahydropyrimidinium chloride H2L2 以同樣的方式與胺基稀土反應(yīng),也得到了結(jié)構(gòu)類似的胺基稀土配合物L(fēng)2KLnN"3(Ln=Y,2a;Nd,2b)。單晶X-射線衍射分析表明這四種配合物均為單個甲苯溶劑分子配位的單分子配合物結(jié)構(gòu),配合物中存在金屬鉀和稀土元素兩種金屬離子。其中鉀離子與配體上的卡賓結(jié)構(gòu)成鍵,稀土金屬帶著三個六甲基二硅胺基基團與配體上的酚氧基相連,不同的稀土金屬釔和釹均可以得到相同結(jié)構(gòu)的配合物。同時,對于含有釔離子的配合物1a、2a做了核磁共振表征,且用DFT方法模擬了它們的結(jié)構(gòu),由NBO計算結(jié)果得到了兩種結(jié)構(gòu)的電荷分布和成鍵軌道構(gòu)成。通過原位核磁的方式表征了在不同加料順序時,制備配合物1a和1b可能發(fā)生的不同的反應(yīng)過程。單酚取代氮雜環(huán)卡賓胺基稀土配合物1a-2b可以單組份有效催化ε-已內(nèi)酯開環(huán)聚合反應(yīng),得到高分子量的聚合產(chǎn)物。在異丙醇存在下催化ε-已內(nèi)酯聚合反應(yīng),聚合過程與異丙醇的加入量有關(guān),當(dāng)加入10倍當(dāng)量的異丙醇參與聚合反應(yīng)時,聚合體系呈現(xiàn)出可控聚合的特征。
[Abstract]:A series of monophenol-substituted carbene ligand precursors were prepared and their structures were characterized by nuclear magnetic resonance spectroscopy (NMR) and elemental analysis. Two kinds of tetrahydropyrimidine ligand precursors were selected to coordinate with hexamethylamino rare earth compounds. Four novel aza-heterocyclic carbenamine rare earth complexes were prepared and analyzed by single crystal X-ray diffraction. The exact structure of the complex was characterized by nuclear magnetic resonance spectroscopy. The complexes were used to catalyze the ring-opening polymerization of 蔚 -caprolactone. It was found that these complexes could effectively catalyze the ring-opening polymerization of 蔚 -caprolactone, either in a one-component system or in a two-component system composed of isopropanol. The amino rare earth complex (L1KLnN "3LNNNX Y1a NdNdN) containing the structure of carbene and potassium was synthesized by the reaction of naphthol substituted N-heterocyclic carbene ligands 3-hexamethylenyl-methyl-1-mesityl-3-tetrahydropyrimidinium chloride H2L1 with hexamethylsilymidinium Ln [N(SiMe3)2] 3. In the same way, the phenol-substituted N-heterocyclic carbene ligand precursor 3-trichloro-2-hydroxybenzyl-1-mesityl-3azyl-3-tetrahydropyrimidinium chloride H2L2 reacted with amino rare earth elements in the same way, and a similar Amino rare earth complex L2KLnN "3 LnnCY _ 2a Nd2b" was obtained. The single crystal X-ray diffraction analysis shows that the four complexes are monomolecular complexes coordinated by a single toluene solvent, and there are two metal ions, potassium metal and rare earth elements, in the complexes. Potassium ions bond with carbene structure on ligands, rare earth metals with three hexamethyldisilylamino groups are linked to phenoxy groups on ligands, and different rare earth metal yttrium and neodymium can all get the same structure complexes. At the same time, the complex 1a ~ 2a containing yttrium ion was characterized by NMR, and their structures were simulated by DFT method. The charge distribution and bonding orbitals of the two structures were obtained by NBO calculation. The different reaction processes of 1a and 1b were characterized by in situ NMR. Monophenol substituted aza-heterocyclic carbenamine rare earth complex 1a-2b can effectively catalyze ring-opening polymerization of 蔚 -caprolactone and obtain high molecular weight polymerization products. The polymerization process of 蔚 -caprolactone in the presence of isopropanol is related to the amount of isopropanol added. When isopropanol of 10 times equivalent is added to the polymerization, the polymerization system exhibits the characteristics of controllable polymerization.
【學(xué)位授予單位】：浙江大學(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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