【作者】 姚伟；

【导师】 母瀛；

【作者基本信息】 吉林大学 ， 有机化学， 2008， 博士

【摘要】 本论文首次合成了四个系列二十七个未见文献报道的胺亚胺金属配合物,并通过元素分析、核磁共振谱和X-射线单晶衍射等测试手段对所合成的化合物进行了结构表征。对其中铝、锌十二个金属配合物进行了催化己内酯开环聚合的性质的测定,研究了它们的聚合条件及机理,初步研究了三个镍配合物催化环氧丙烷与二氧化碳偶联反应的性能,并研究了四价铬化合物的生成机理及催化乙烯聚合的条件。利用乙二胺和邻氟苯甲醛反应生成西佛碱,再与取代的胺锂盐反应得到两个乙基桥联的胺亚胺配体,[ortho-C₆H₄（NHAr）CH=N]₂CH₂CH₂ （Ar = 2,6-Me₂C₆H₃, LA1H₂; Ar = 2,6-iPr2C₆H₃, LA₂H₂）。利用上述两种配体分别与AlMe₃,ZnEt₂在甲苯中反应合成了一系列单核铝,异核铝锌,同核铝,同核锌金属配合物,并对配体和配合物进行元素分析和核磁表征。得到五个单晶,并测得了它们的晶体结构。利用以上配合物作为催化剂在苄醇存在下催化己内酯开环聚合,反应活性很高,具有活性聚合的特点。根据文献方法合成了一系列胺亚胺配体,ortho-C₆H₄（CH=NAr1）（NHAr²） [Ar¹ = C₆H₅, Ar² = C₆H₅ （LB1H）; Ar¹ = 2,6-Me₂C₆H₃, Ar² = 2,6-Me₂C₆H₃ （LB2H）; Ar¹ = 2,6-Et+2C₆H₃, Ar²= 2,6-Et₂C₆H₃ （LB3H）; Ar¹ = 2,6-iPr2C₆H₃, Ar² = 2,6- Me₂C₆H₃ （LB4H）; Ar1 = 2,6-iPr₂C₆H₃, Ar²= 2,6-Et₂C₆H₃ （LB5H）; Ar₁ = 2,6-iPr₂- C₆H₃, Ar²=2,6-iPr₂C₆H₃ （LB₆H）]。利用上述配体与AlMe₃在己烷中反应合成了一系列单核铝的配合物,并对配体和配合物进行元素分析和核磁表征。利用以上配合物作为催化剂在苄醇存在下催化己内酯开环聚合,反应活性较高,具有活性聚合的特点。利用手性二胺和邻氟苯甲醛反应生成西佛碱,再与取代的胺锂盐反应得到三个手性胺亚胺配体,[ortho-C₆H₄（NHAr）CH=N]2C₆H₁₀ [（1R,2R）-L_C1H₂ （Ar = 2,6-Me₂C₆H₃）, （1R,2R）-LC₂H₂ （Ar = 2-MeC₆H₄）, （1R,2R）-LC₃H₂ （Ar = 4-Me- C₆H₄）]。利用上述手性配体先后与丁基锂,金属氯化物反应得到相应的金属配合物,我们先后合成了Zr,Cr,Co,Ni,Cu五种金属配合物,并对配体和配合物进行元素分析和核磁表征。得到六个单晶,并测得了它们的晶体结构。利用镍配合物作为催化剂在季铵盐存在下催化环氧丙烷与二氧化碳偶联反应,反应活性较高。利用2,6-二异丙基苯胺和邻氟苯甲醛反应生成西佛碱,再与邻苯二胺的双胺锂盐反应得到一个四齿胺亚胺配体, [ortho-C₆H₄- （CH=NC₆H₃ⁱPr₂-2,6）NH]2C₆H₄ （LDH₂）。利用上述配体先后与丁基锂,氯化亚铬反应得到一个非常新颖的四价铬的配合物,对配体和配合物进行元素分析和核磁表征,得到了这个四价铬的单晶,并测得了它的晶体结构。利用这个四价铬的配合物作为催化剂在AlⁱBu₃/Ph₃CB（C₆F₅）₃活化下催化乙烯聚合,反应活性中等,聚合物的分子量超过100万。更多还原

【Abstract】 Salen ligands and their transition metal complexes have been extensively explored as catalysts in the last few decades. Many of these complexes have been found to be excellent catalysts for a number of reactions. A catalyst with proper ligand and proper metal center can catalyze a proper reaction. From structural point of view, there are two substituents at the ortho-position of the coordinating O atoms in the salen ligand. The steric effect of the substituents on the coordinating atoms in the ligands should be larger than those in the salen ligands. With such a consideration in mind, we have designed three classes of tetra-azane chelating ligands and their transition metal complexes in which there are two substituents on the coordinating N atoms. The steric and electronic effect of the two substituents in the new ligands should be better than those in the salen ligands and the PPNN ligands that modified the catalytic activity and selectivity.Ligands [ortho-C₆H₄（NHAr）CH=N]₂CH₂CH₂ (Ar = 2,6-Me₂-C₆H₃, L_A1H₂; Ar = 2,6-ⁱPr₂C₆H₃, LA₂H₂) were prepared by condensation between ethylenediamine with two equivalents of 2- fluorobenzaldehyde in methanol, followed by reaction with two equivalents of lithium salt of substituted aniline in THF. Treatment of L_A1H₂ with one equiv of AlMe₃ gives the tetracoordinated monometallic complex L_A1HAlMe₂. The hetrobimetallic complex L_A1ZnEtAlMe₂ was prepared by reaction of one equiv of ZnEt₂ with the complex L_A1HAlMe₂ in toluene. Treatment of the ligand L_A1H₂ or L_A2H₂ with two equiv of AlMe₃ gives the bimetallic complex L_A1（AlMe₂）₂ or L_A2（AlMe₂）₂, and reaction of L_A1H₂ or L_A2H₂ with two equiv of ZnEt2 leads to the formation of bimetallic complex L_A1（ZnEt）₂ or L_A2（ZnEt）₂ , respectively. The complexes were all characterized by elemental analyses and 1H and 13C NMR spectroscopy. Crystal structures of complexes L_A1HAlMe2, L_A1ZnEtAlMe2, L_A1（AlMe2）2, L_A2（AlMe2）2, and L_A1（ZnEt）2 were determined by single-crystal X-ray diffraction. All of the complexes are efficient catalysts for ring-opening polymerization ofε-caprolactone in the presence of benzyl alcohol and catalyze the polymerization ofε-caprolactone in living fashion yielding polymers with a narrow polydispersity index.Anilido-imine ligands ortho-C₆H₄（CH=NAr1）（NHAr²） [Ar1 = C₆H₅, Ar² = C₆H₅ （LB1H）; Ar1 = 2,6-Me2C₆H₃, Ar² = 2,6-Me2C₆H₃ （LB2H）; Ar1 = 2,6-Et2C₆H₃, Ar²= 2,6-Et2C₆H₃ （LB3H）; Ar1 = 2,6-iPr2C₆H₃, Ar² = 2,6-Me2C₆H₃ （LB4H）; Ar1 = 2,6-iPr2C₆H₃, Ar²= 2,6-Et2C₆H₃ （LB5H）; Ar1 = 2,6-iPr₂C₆H₃, Ar²=2,6-iPr2C₆H₃ （LB₆H）] were synthesized according to the literature procedure. Treatment of the ligands with AlMe₃ in hexane gives the desired anilido-imine Al complexes. The anilido-imine Al complexes were all characterized by elemental analyses and 1H NMR spectroscopy. All of these anilido-imine Al complexes are efficient catalysts for ring-opening polymerization ofε-caprolactone in the presence of benzyl alcohol and catalyze the polymerization ofε-caprolactone in living fashion.Ligands [ortho-C₆H₄（NHAr）CH=N]₂C₆H₍10 [（1R,2R）-L_C1H₂ （Ar = 2,6-Me₂C₆H₃）, （1R,2R）-LC₂H₂ （Ar = 2-MeC₆H₄）, （1R,2R）-L_C3H₂ （Ar = 4-MeC₆H₄）]were prepared by condensation between chiral cylclohexane diamine with two equivalents of 2- fluorobenzaldehyde in methanol, followed by reaction with two equivalents of lithium salt of substituted aniline in THF. The transition metal complexes [L_C1ZrCl₂, L_C2ZrCl₂, L_C3ZrCl₂, L_C1CrCl, L_C2CrCl, L_C3CrCl, L_C1Co, L_C2Co, L_C3Co, L_C1Ni, L_C2Ni, L_C3Ni, L_C1Cu, L_C2Cu, L_C3Cu] were synthesized in good yields via metathesis of MCl₂ （M=ZrCl₂（THF）2, Co, Ni（DME）, Cu） with the lithium salt of the corresponding ligands, respectively. Molecular structure of （1R,2R）-L¹H₂, L_C1ZrCl₂, L_C1CrCl, L_C1Co, L_C1Ni, L_C3Ni and L_C1Cu were determined by X-ray crystallography. All of the Ni complexes are efficient catalysts for the coupling reaction of propylene oxide with CO2 in the presence of a quaternary ammonium salt.The new ligand [ortho-C₆H₄（CH=NC₆H₃iPr2-2,6）NH]2C₆H₄ （LDH₂） was synthesized via a nucleophilic displacement of fluorine in ortho-C₆H₄F- （CH=NC₆H₃iPr2-2,6） by dilithium salt of 1,2-benzendiamine in THF. Reaction of the dilithium salt of LDH₂ with CrCl₂（THF） in THF gives the six-coordinated Cr（IV） complex. Molecular structure of the Cr（IV） complex was determined by X-ray crystallography. Upon activation with AliBu3 and Ph₃CB（C₆F₅）₄ as cocatalysts, the Cr（IV）complex was found to be active towards ethylene polymerization to give solid polyethylenes. The activity is moderate in room temperature though the molecular weight of the polyethylene is very high （Mv: 1650000）.更多还原