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

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Abstract

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= η 5-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.

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Authors and Affiliations

  1. Department of Chemistry, Fudan University, Shanghai, 200433, China

    Ping Hu, ZhenHua Li & GuoXin Jin

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  1. Ping Hu
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  2. ZhenHua Li
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  3. GuoXin Jin
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Correspondence to GuoXin Jin.

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Dedicated to Professor Qian Changtao on the occasion of his 80th birthday.

JIN GuoXin received his PhD from Nanjing University in 1987, after a post-doctoral work at University of Bayreuth, Germany, he joined Changchun Institute of Applied Chemistry, Chinese Academy of Sciences in 1996 as a professor. In 2001 he moved to Shanghai and held the Chair Professor (CheungKong Scholarship) of Inorganic Chemistry at Fudan University. His research interests are in organometallic chemistry, particularly in carborane chemistry, organometaliic macrocyclic architecture and the catalysts for olefin polymerization.

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Hu, P., Li, Z. & Jin, G. Ethylene (co-)polymerization by long-lifetime half-sandwich zirconium catalyst bearing a [SSO]-carborane ligand. Sci. China Chem. 57, 1137–1143 (2014). https://doi.org/10.1007/s11426-014-5075-1

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