受限几何型金属化合物的合成和催化性能  

Synthesis and Catalytic Property of Constrained Geometric Structural Metal Compounds

作　　者：张公平 席鑫 蒋文军 陈志康 朱红平[1] ZHANG Gong-Ping;XI Xin;JIANG Wen-Jun;CHEN Zhi-Kang;ZHU Hong-Ping(State Key Laboratory of Physical Chemistry of Solid Surfaces,Xiamen University,Xiamen,Fujian 361005,China)

机构地区：[1]固体表面物理化学国家重点实验室,厦门大学化学化工学院,厦门361005

出　　处：《无机化学学报》2020年第12期2249-2260,共12页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21673191,21972112)资助项目。

摘　　要：通过筛选合成路线和方法制备了3种桥联芴基-芳胺基化合物Me2Si[(Flu)H]NH-2,6-iPr2C6H3(L1)、Me2Si[2,7-tBu2Flu(H)]NH-2,6-iPr2C6H3(L2)和Me2Si[2,7-tBu2Flu(H)]NH-2,4,6-Me3C6H2)(L3),分别与第四族金属氯化物MCl4反应制备了4种受限几何结构的茂金属化合物[Me2Si(Flu)(N-2,6-iPr2C6H3)]ZrCl2(THF)2(1)、[Me2Si(2,7-tBu2Flu)(N-2,6-iPr2C6H3)]TiMe2(2)、[Me2Si(2,7-tBu2Flu)(N-2,4,6-Me3C6H2)]TiMe2(3)和[Me2Si(2,7-tBu2Flu)(N-2,6-iPr2C6H3)]HfMe2(4)。化合物L1~L3和1~4都经过谱学和元素分析表征,其中1~3还经过X射线衍射单晶结构确认。在AliBu3和(Ph3C)+[B(C6F5)4]-双助剂作用下研究了1~4分别催化乙烯/1-辛烯聚合性能,结果显示茂金属单活性中心作用特点以及1-辛烯的共聚效果。考察和比较了其它3种受限几何钛化合物[Me2Si(C5Me4)(NtBu)]TiCl2、[Me2Si(Ind)(NtBu)]TiCl2和[Me2Si(Flu)(NtBu)]TiMe2的催化性能;讨论了1~4的结构和催化作用的关联性。Three ansa-fluorenyl-arylamino ligand compounds Me2Si[(Flu)H]NH-2,6-iPr2C6H3(L1),Me2Si[2,7-tBu2Flu(H)]NH-2,6-iPr2C6H3(L2)and Me2Si[2,7-tBu2Flu(H)]NH-2,4,6-Me3C6H2)(L3)were prepared by means of selection of the suitable synthetic route and method.The reactions using L1~L3 each with groupⅣMCl4 by nBuLi-lithiation followed with metathesis yielded the constrained geometric metallocene compounds[Me2Si(Flu)(N-2,6-iPr2C6H3)]ZrCl2(THF)2(1),[Me2Si(2,7-tBu2Flu)(N-2,6-iPr2C6H3)]TiMe2(2),[Me2Si(2,7-tBu2Flu)(N-2,4,6-Me3C6H2)]TiMe2(3)and[Me2Si(2,7-tBu2Flu)(N-2,6-iPr2C6H3)]HfMe2(4).The operation for synthesis of all these compounds was conducted by using moisture-and oxygen-free Schlenk technology.Compounds L1~L3 and 1~4 have all been characterized by NMR spectroscopy and elemental analysis,of which 1~3 further by X-ray crystallography.In combination of AliBu3 and(Ph3C)+[B(C6F5)4]-as the co-catalysts,the catalytic properties of 1~4 were investigated on ethylene/1-octene polymerization.The results obtained indicate a single-site catalysis(SSC)with 1-octene copolymerized.The catalytic properties of related titanium compounds[Me2Si(C5Me4)(NtBu)]TiCl2,[Me2Si(Ind)(NtBu)]TiCl2 and[Me2Si(Flu)(NtBu)]TiMe2 were also examined.The correlations between the structures of 1~4 and the catalytic property are discussed.CCDC:1975179,1;1975180,2;1986175,3;1986178,5.

关 键 词：桥联芴基-芳胺基配体 限制性几何构型催化剂 乙烯/1-辛烯聚合 催化反应条件 

分 类 号：O614.411[理学—无机化学] O614.412[理学—化学]