Citation: ZHANG Gong-Ping, XI Xin, JIANG Wen-Jun, CHEN Zhi-Kang, ZHU Hong-Ping. Synthesis and Catalytic Property of Constrained Geometric Structural Metal Compounds[J]. Chinese Journal of Inorganic Chemistry, ;2020, 36(12): 2249-2260. doi: 10.11862/CJIC.2020.261 shu

Synthesis and Catalytic Property of Constrained Geometric Structural Metal Compounds

State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, Fujian 361005, China

Corresponding author: JIANG Wen-Jun, jiangwenj@stu.xmu.edu.cn ZHU Hong-Ping, hpzhu@xmu.edu.cn
Received Date: 28 July 2020
Revised Date: 28 September 2020

Figures(9)

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 group Ⅳ MCl₄ 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)(N^tBu)]TiCl₂, [Me₂Si(Ind)(N^tBu)]TiCl₂ and [Me₂Si(Flu)(N^tBu)]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.
- ansa-fluorenyl-arylamino ligand,
- constrained geometric catalyst,
- ethylene/1-octene polymerization,
- catalytic reaction condition
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