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Catalysts 2013, 3(1), 261-275; doi:10.3390/catal3010261

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

1,*  and 1
1 State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China 2 University of the Chinese Academy of Sciences, Changchun Branch, Changchun 130022, China
* Author to whom correspondence should be addressed.
Received: 28 December 2012 / Revised: 8 February 2013 / Accepted: 17 February 2013 / Published: 6 March 2013
(This article belongs to the Special Issue Molecular Catalysis for Precise Olefin Polymerization)
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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.
Keywords: copolymerization; catalysts; ethylene copolymerization; catalysts; ethylene
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Tang, X.-Y.; Liu, J.-Y.; Li, Y.-S. Phosphine-Thiophenolate Half-Titanocene Chlorides: Synthesis, Structure, and Their Application in Ethylene (Co-)Polymerization. Catalysts 2013, 3, 261-275.

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