毕业设计（论文）-四价铈配合物的合成研究.doc

四价铈配合物的合成研究 摘 要 以硝酸铈铵、叔丁醇钠、胍基钠和三甲基硅胺基钠为原料，四氢呋喃为溶剂合成了以胍基（Gua）/叔丁氧基，二（三甲基硅）胺（TMS2N）/叔丁氧基为配位体，铈（Ⅳ）为配位离子的混配型配合物。通过配位滴定元素分析和红外对其组成进行了分析。经配位滴定分析,所得产物Ce元素含量与目标产物基本相符。经红外表征证明,产物中含有胍基和二（三甲基硅）胺基。初步证明产物为(Gua)Ce(OtBu)3、(Gua)2Ce(OtBu)2、(Gua)3Ce(OtBu)、(TMS2N)Ce(OtBu)3、(TMS2N)2Ce(OtBu)2和(TMS2N)3Ce(OtBu)。这6种对ε-己内酯聚合均有一定催化活性，但活性较低。活性从大到小变化顺序：(Gua)3Ce(OtBu) (Gua)Ce(OtBu)3 (Gua)2Ce(OtBu)2 (TMS2N)3Ce(OtBu) (TMS2N)Ce(OtBu)3 (TMS2N)2Ce(OtBu)2。配体对配合物催化性能影响极大。胍基比胺基更有利于促进配合物的催化活性。 Study on Synthesis of Cerium (Ⅳ) Complexes Abstract A series of tetravalent cerium complexes were synthesized with mixed ligands of guanidinate / tert-butoxide and bis(trimethylsilyl)amide / tert-butoxide, starting from ceric ammonium nitrate, tert-butoxide sodium and guanidinate sodium or bis(trimethylsilyl)amide sodium. These complexes were analyzed by complexo-metric titration and IR. The complexo-metric titration indicates that the Ce contents in complexes are consistent with those expected. The IR indicates that the products contain guanidinate ligand or bis(trimethylsilyl)amino ligand. These results supported the suggestion that products are (Gua)Ce(OtBu)3, Gua)2Ce(OtBu)2, (Gua)3Ce(OtBu), (TMS2N)Ce(OtBu)3, (TMS2N)2Ce(OtBu)2 and (TMS2N)3Ce(OtBu), respectively. These six complexes showed some catalytic activity for the polymerization of ε-caprolactone. The activity decreases in the order: (Gua)3Ce(OtBu) (Gua)Ce(OtBu)3 (Gua)2Ce(OtBu)2 (TMS2N)3Ce(OtBu) (TMS2N)Ce(OtBu)3 (TMS2N)2Ce(OtBu)2. The ligands of complexes have great influence upon the catalytic activity. Guanidinate ligand is more favorable for the Ce(IV) tert-butoxide than bis(trimethylsilyl)amino ligand. Keywords rare earth; cerium(IV); complex; polymerization 目录 第一章 绪论 1 1.1 引言 1 1.2 烷氧Ce(IV)配合物 2 1.3 立题 7 第二章 实验部分 7 2.1 操作、原料、仪器 7 2.2 实验原料 7 2.3 实验仪器 8 2.4 分析 8 2.5 叔丁醇钠(ButONa)的制备 8 2.6 (Me3Si)2NDCCNa (GuaNa)的制备 9 2.7 催化CL聚合 9 2.8 (Gua)Ce(OBut)3的制备 9 2.9 (Gua)2Ce(OBut)2的制备 10 2.10 (Gua)3Ce(OBut)的制备 10 2.11 (TMS2N)Ce(OB