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Formation of Dinuclear Titanium and Zirconium Complexes by Olefin Metathesis—Catalytic Preparation of Organometallic Catalyst Systems
Author(s) -
Cano Sierra Jesus,
Hüerländer Doris,
Hill Michael,
Kehr Gerald,
Erker Gerhard,
Fröhlich Roland
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200304789
Subject(s) - chemistry , catalysis , medicinal chemistry , propene , metathesis , olefin fiber , homogeneous catalysis , toluene , yield (engineering) , imes , titanium , zirconium , polymerization , carbene , polymer chemistry , organic chemistry , materials science , metallurgy , polymer
Abstract The titanium complex [(C 5 H 4 allyl)TiCl 3 ] ( 2 ) undergoes olefin metathesis coupling when treated with 3 mol % of [Cl 2 (L 1 )(L 2 )RuCHPh] (L 1 =L 2 =PCy 3 , 4 a ; L 1 =PCy 3 , L 2 =(H 2 IMes), 4 b ) to yield the dimetallic complex [Cl 3 Ti(C 5 H 4 )‐CH 2 CHCHCH 2 ‐(C 5 H 4 )TiCl 3 ] ( 5 ). The allyl‐substituted titanocene complex [Cp(C 5 H 4 allyl)TiCl 2 ] ( 3 ) analogously yields the dimetallic system 6 when treated with 4 . The ansa‐zirconocene complex [Me 2 Si(C 5 H 4 )(C 5 H 3 allyl)ZrCl 2 ] ( 7 ) cleanly yields the analogous dimetallic coupling product 8 (>95 % isomerically pure), when treated with catalytic amounts of 4 b in toluene. Complex 8 gives an active homogeneous ethene or propene polymerization catalyst, especially at elevated temperatures, when treated with excess methylalumoxane.