%0 Journal Article
%T Phosphine-Thiophenolate Half-Titanocene Chlorides: Synthesis, Structure, and Their Application in Ethylene (Co-)Polymerization
%A Xiao-Yan Tang
%A Jing-Yu Liu
%A Yue-Sheng Li
%J Catalysts
%D 2013
%I MDPI AG
%R 10.3390/catal3010261
%X A series of novel half-titanocene complexes CpTiCl 2[S-2-R-6-(PPh 2)C 6H 3] (Cp = C 5H 5, 2a, R = H; 2b, R = Ph; 2c, R = SiMe 3) have been synthesized by treating CpTiCl 3 with the sodium of the ligands, 2-R-6-(PPh 2)C 6H 3SNa, 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 2 a¨Cb were further confirmed by X-ray crystallography. Complexes 2 a¨Cb 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 ¨Cc were investigated as the catalysts for ethylene polymerization and copolymerization of ethylene with norbornene in the presence of MMAO or Ph 3CB(C 6F 5) 4/ iBu 3Al 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.
%K copolymerization
%K catalysts
%K ethylene
%U http://www.mdpi.com/2073-4344/3/1/261