SYNTHESIS OF ZIRCONOCENE SILSESQUIOXANE COMPLEXES AND THEIR ETHENE POLYMERIZATION ACTIVITY IN SYSTEMS WITH METHYLALUMINOXANE

0351870 - ÚFCH JH 2011 RIV CZ eng J - Journal Article
Varga, V. - Pinkas, Jiří - Gyepes, R. - Štěpnička, P. - Horáček, Michal - Bastl, Zdeněk - Mach, Karel
SYNTHESIS OF ZIRCONOCENE SILSESQUIOXANE COMPLEXES AND THEIR ETHENE POLYMERIZATION ACTIVITY IN SYSTEMS WITH METHYLALUMINOXANE.
Collection of Czechoslovak Chemical Communications. Roč. 75, č. 1 (2010), s. 105-119. ISSN 0010-0765
R&D Projects: GA AV ČR KAN100400701; GA MŠMT(CZ) LC06070
Institutional research plan: CEZ:AV0Z40400503
Keywords : zircone * zirconocene * ethene polymerization
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 0.853, year: 2010

Protocols for obtaining defined zirconocene complexes with polyhedral oligomeric silsesquioxanes with mono-, di-, and trisilanol functionality (SIPOSS, DIPOSS, and TRIPOSS) were established. The TRIPOSS silanolates binding one zirconocene and one chlorozirconocene moiety, [{(c-C5H9)(7)Si7O9O3}Zr2Cl(eta(5)-C5H4R)(4)] (1, R = Bu; 2, R = H), were obtained by reacting the silanol with the respective zirconocene dichloride and triethylamine in CH2Cl2 in a 1.0:3.0:3.0 molar ratio, an excess of the zirconocene dichloride being required to suppress intramolecular dehydration of TRIPOSS. The related SIPOSS complex, [{(c-C5H9)(7)Si8O12O}(2)Zr(eta(5)-C5H4Bu)(2)] (3), was prepared similarly at the stoichiometric ratio of [ZrCl2(eta(5)-C5H4Bu)(2)]/ SIPOSS/NEt3 equal to 1.0:2.0:2.0. When employed in the 1.0:1.0:1.0 ratio, the same reagents afforded only the impure complex [{(c-C5H9)(7)Si8O12O}ZrCl(eta(5)-C5H4Bu)(2)] (4), contaminated with 3 and unreacted [ZrCl2(eta(5)-C5H4Bu)(2)].
Permanent Link: http://hdl.handle.net/11104/0191518