Formation of dinuclear titanium and zirconium complexes by olefin metathesis--catalytic preparation of organometallic catalyst systems

The titanium complex (C(5)H(4)bond;allyl)TiCl(3)] (2) undergoes olefin metathesis coupling when treated with 3 mol % of Cl(2)(L(1))(L(2))Ru=CHPh] (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)CH=CHCH(2)-(C(5)H(4))TiCl(3)] (5). The allyl-substituted titanocene complex Cp(C(5)H(4)bond;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)bond;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.