吲哚基NCN钳型钛族金属配合物的合成及其催化苯乙烯聚合反应
Indolyl-based NCN-pincer titanium group metal complexes: Synthesis and catalytic application for styrene polymerization
作者单位E-mail
刘欢欢 安徽工程大学化学与环境工程学院, 芜湖 241000  
童尧 安徽工程大学化学与环境工程学院, 芜湖 241000  
黄江胜 安徽工程大学化学与环境工程学院, 芜湖 241000 hjsh@ahpu.edu.cn 
王芬华 安徽工程大学化学与环境工程学院, 芜湖 241000  
摘要: 以吲哚为骨架,在吲哚的1位、3位引入2条边臂基团得到了1,3-双取代吲哚基化合物,用丁基锂去质子后与MCl4(M=Ti、Zr、Hf)反应,得到一系列NCN钳型钛、锆、铪金属配合物(3-Ti3-Zr3-Hf)。该系列配合物通过核磁、元素分析及单晶X射线衍射进行了表征。单晶结构显示,金属中心除与3个氯原子配位外,还与配体以κ3NCN的形式配位,形成六配位的八面体构型。考察了该类型配合物在不同助催化体系条件下催化苯乙烯聚合反应的性能。实验发现:在室温下,助催化剂为 AlEt2Cl/(Ph3C)[B(C6F5)4],甲苯为溶剂,单体与催化剂在浓度比300∶1的条件下,不同金属中心配合物都能以高转化率得到聚苯乙烯,其中铪配合物的催化活性最高。催化所得的聚苯乙烯经表征发现均为无规结构,数均分子量为4 000~8 000
关键词: 亚氨基吲哚  NCN钳型  钛族金属配合物  苯乙烯  聚合
基金项目: 安徽省教育厅项目(No.GXXT-2021-052)和安徽工程大学人才培育科研启动基金资助。
Abstract: Indole worked as the backbone and two side arms at the 1-, and 3-positions were introduced to obtain a 1, 3-di-functionalized indolyl compound. After the deprotonation by BuLi, it was reacted with MCl4 (M=Ti, Zr, Hf) to form a series of NCN-pincer type titanium group metal complexes (3-Ti, 3-Zr, 3-Hf). The complexes were characterized by NMR, elemental analysis, and single-crystal X-ray diffraction. The single-crystal structures revealed that the metal center bonds with the ligand in κ3NCN modes and three chlorine atoms to form a six-coordinated distorted octahedral configuration. Styrene polymerization was investigated with 3-Ti, 3-Zr, and 3-Hf using aluminum alkyls and borate reagents as cocatalysts when the concentration ratio of the monomer to the complex was 300∶1. It was found the complexes of different metal centers could efficiently catalyze styrene polymerization with high conversion under room temperature and using AlEt2Cl/(Ph3C)[B(C6F5)4] as cocatalysts, moreover, the hafnium complex displayed the higher activity. The obtained polystyrene was characterized by gel permeation chromatography (GPC) and 13C NMR. The results showed the polymer was atactic and had a low number-average molecular weight ($\bar{M}_n$=4 000-8 000).
Keywords: imino substituted indole  NCN-pincer type  titanium group metal complex  styrene  polymerization
投稿时间:2024-03-11 修订日期:2024-05-18
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刘欢欢,童尧,黄江胜,王芬华.吲哚基NCN钳型钛族金属配合物的合成及其催化苯乙烯聚合反应[J].无机化学学报,2024,40(7):1261-1269.
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