Phosphine-Thiophenolate Half-Titanocene Chlorides: Synthesis, Structure, and Their Application in Ethylene (Co-)Polymerization

Catalysts

Xiao-Yan Tang¹  Jing-Yu Liu¹ 

[1] State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China; E-Mails:

关键词: copolymerization;    catalysts;    ethylene;   

DOI  :  10.3390/catal3010261

来源: mdpi

【 摘 要 】

A series of novel half-titanocene complexes CpTiCl₂[S-2-R-6-(PPh₂)C₆H₃] (Cp = C₅H₅, 2a, R = H; 2b, R = Ph; 2c, R = SiMe₃) have been synthesized by treating CpTiCl₃ with the sodium of the ligands, 2-R-6-(PPh₂)C₆H₃SNa, which were prepared by the corresponding ligands and NaH. These complexes have been characterized by ¹H, ¹³C and ³¹P NMR as well as elemental analyses. Structures for 2a–b were further confirmed by X-ray crystallography. Complexes 2a–b adopt five-coordinate, distorted square-pyramid geometry around the titanium center, in which the equatorial positions are occupied by sulfur and phosphorus atoms of the chelating phosphine-thiophenolate and two chlorine atoms, and the cyclopentadienyl ring is coordinated on the axial position. The complexes 2a–c were investigated as the catalysts for ethylene polymerization and copolymerization of ethylene with norbornene in the presence of MMAO or Ph₃CB(C₆F₅)₄/ⁱBu₃Al as the cocatalyst. All complexes exhibited low to moderate activities towards homopolymerization of ethylene. However, they displayed moderate to high activities towards copolymerization of ethylene with norbornene.

【 授权许可】

CC BY   
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