- Preparation and characterization of half-sandwich (pentamethylcyclopentadienyl)(triflato)titanium(IV) complexes: Solid-state structural motifs and catalysis studies
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Half-sandwich (pentamethylcyclopentadienyl)(triflato)titanium(IV) complexes of the type [Ti(Cp*)-(TfO)2X] (X=MeO (1), Me (2), 2,4,6-Me3C6H2O (5)) or [Ti(Cp*)(o-OC6H4O)(TfO)] (7) were readily synthesized via methathesis of the corresponding chloride complexes with silver triflate (Cp* = (η5-1,2,3,4,5- pentamethylcyclopenta-2,4-dien-1-yl)). In addition, the complex 3 with X = OH was prepared by controlled hydrolysis of 2. The solid-state structures of these new complexes were determined by single-crystal X-ray-diffraction techniques. Three different structural motifs were identified; 1, 2, 3, and 7 are dimeric, while 5 is monomeric. The complexes were screened for their ability to stereospecifically polymerize styrene under homogeneous conditions. In the absence of activators, such as MAO (methylaluminoxane), 1 and 2 readily catalyzed the formation of atactic polystyrene; a strong dependence on the steric size of X was noted. In the presence of MAO, all of the complexes showed high activity and strong preference for the synthesis of syndiotactic polystyrene that was superior to that of [TiCl3(Cp*)]/MAO.
- Ngo, Silvana C.,Toscano, Paul J.,Welch, John T.
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p. 3366 - 3382
(2007/10/03)
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- Synthesis of various nonbridged titanium(IV) cyclopentadienyl-aryloxy complexes of the type CpTi(OAr)X2 and their use in the catalysis of alkene polymerization. Important roles of substituents on both aryloxy and cyclopentadienyl groups
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Various titanium complexes of the type Cp′Ti-(OAr)Cl2 (Cp′ = cyclopentadienyl; OAr = aryloxy) could be prepared in high yields from Cp′TiCl3. These complexes show remarkable catalytic activities for alkene polymerization with MAO or
- Nomura, Kotohiro,Naga, Naofumi,Miki, Misao,Yanagi, Kazunori,Imai, Akio
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p. 2152 - 2154
(2008/10/08)
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