Ethylene (co-)polymerization by long-lifetime half-sandwich zirconium catalyst bearing a [SSO]-carborane ligand  

作　　者：HU Ping LI ZhenHua JIN GuoXin 

机构地区：[1]Department of Chemistry, Fudan University

出　　处：《Science China Chemistry》2014年第8期1137-1143,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (91122017, 21374019);the Shanghai Science and Technology Committee (13JC1400600, 13DZ2275200);the Program for Changjiang Scholars and Innovative Research Team in University (IRT1117)

摘　　要：Half-sandwich zirconium complex 3 containing tridentate carborane [S,S,O] ligand 2 [(HOC6H2R2-4,6)(CH2)SC(B10H10) C(Ph)2P=S, R=tBu] was synthesized by the reaction of CpZrCl3(Cp=η5-C5H5) with sodium salt of ligand 2. Zirconium complex 3 was characterized by elemental and NMR analyses. DFT calculations were also performed on complex 3 to analyze the stereochemistry. The results from DFT calculations indicate that structure S1, in which no sulfur atom bonds to the zirconium atom, exists at the lowest energy level. In the presence of methylaluminoxane(MAO), complex 3 exhibited good catalytic activities for ethylene polymerization and long life-time up to 10 h. Moreover, the complex 3/MAO system displayed excellent catalytic activities toword ethylene copolymerization with 1-hexene or polar olefins.Half-sandwich zirconium complex 3 containing tridentate carborane [S,S,O] ligand 2 [（HOC6H2R2-4,6）（CH2）SC（B10H10） C（Ph）2P=S, R=tBu] was synthesized by the reaction of CpZrCl3（Cp=η5-C5H5） with sodium salt of ligand 2. Zirconium complex 3 was characterized by elemental and NMR analyses. DFT calculations were also performed on complex 3 to analyze the stereochemistry. The results from DFT calculations indicate that structure S1, in which no sulfur atom bonds to the zirconium atom, exists at the lowest energy level. In the presence of methylaluminoxane（MAO）, complex 3 exhibited good catalytic activities for ethylene polymerization and long life-time up to 10 h. Moreover, the complex 3/MAO system displayed excellent catalytic activities toword ethylene copolymerization with 1-hexene or polar olefins.

关 键 词：half-sandwich zirconium complex ethylene （co-）polymerization carborane ligand 

分 类 号：O643.36[理学—物理化学]