2-((2,6-二甲基苯基)氨基)乙醇铝和锌配合物的合成、结构及催化活性  

Synthesis,structures,and catalytic activity of aluminum and zinc complexes chelated by 2⁃((2,6⁃dimethylphenyl)amino)ethanolate

作　　者：刘安求[1] 蔺隆 张德志 雷珺宇 王科峰[2] 张蔚[2] 庄俊鹏[1] 郝海军[1] LIU Anqiu;LIN Long;ZHANG Dezhi;LEI Junyu;WANG Kefeng;ZHANG Wei;ZHUANG Junpeng;HAO Haijun(Department of Organic Chemistry,College of Chemistry,Beijing University of Chemical Technology,Beijing 100029,China;Petrochemical Research Institute,PetroChina Company Limited,Beijing 100195,China;PetroChina Harbin Petrochemical Company,Harbin 150056,China)

机构地区：[1]北京化工大学化学学院有机化学系,北京100029 [2]中国石油天然气股份有限公司石油化工研究院,北京100195 [3]中国石油天然气股份有限公司哈尔滨石化分公司,哈尔滨150056

出　　处：《无机化学学报》2024年第4期791-798,共8页Chinese Journal of Inorganic Chemistry

基　　金：中国石油天然气股份有限公司石油化工研究院项目资助。

摘　　要：研究了AlMe_(3)和ZnEt_(2)与ArNHCH_(2)CH_(2)OH(HL,Ar=2,6-Me_(2)C_(6)H_(3))的反应,合成了一个双核铝配合物[(Me_(2)Al)(L)]_(2)(1)及一个四核锌配合物[EtZn_(2)(L)_(3)]_(2)(2)。通过核磁、元素分析及单晶X射线衍射分析,对化合物1和2进行了详细的结构表征。结果表明,配合物1在固态下是一个中心对称的具有Al_(2)O_(2)骨架的二聚体,而配合物2存在一个Zn_(4)O_(6)核,其可被视为缺少一对相反顶点的2个并排立方体结构。初步的催化活性测试表明,铝配合物1对ε-己内酯的开环聚合反应没有催化活性,但锌配合物2却表现出很好的催化活性,且能很好地控制所得聚合物的分子量分布在较窄的范围。Treatment of ArNHCH_(2)CH_(2)OH(HL,Ar=2,6-Me_(2)C_(6)H_(3))with AlMe_(3) and ZnEt_(2) resulted in the formation of a bi-aluminum complex,[(Me_(2)Al)(L)]_(2)(1),and a tetra-zinc complex,[EtZn_(2)(L)_(3)]_(2)(2),respectively.They were characterized by elemental analysis,NMR,and single-crystal X-ray diffraction analysis.Complex 1 is a crystallographically centrosymmetric dimer with an Al_(2)O_(2) core in the solid state,while a Zn_(4)O_(6) core is observed in 2,which can be viewed as two side-by-side cubes missing a pair of opposite vertices.Preliminary catalytic activity tests indicated that the aluminum complex 1 was inactive for the ring-opening polymerization(ROP)ofε-caprolactone,while the zinc complex 2 was a highly active initiator for the ROP ofε-caprolactone and could control the molecular weight distribution of the resulted polymers in narrow ranges.CCDC:2304200,1;2304201,2.

关 键 词：开环聚合 铝 锌 氨基乙醇 Ε-己内酯 

分 类 号：O614.31[理学—无机化学] O614.241[理学—化学]