Synthesis and reactivity of trimethylsilyl substituted mono(cyclopentadienyl)titanium alkyl complexes

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Sassmannshausen, J. and Baumgartner, J. (2009) Synthesis and reactivity of trimethylsilyl substituted mono(cyclopentadienyl)titanium alkyl complexes. Kinetics and Catalysis, 50 (5). pp. 676-683. ISSN 0023-1584 (http://dx.doi.org/10.1134/S0023158409050097)

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Abstract

The preparation of a series of titanium half-sandwich compounds [Ti(η5-C5H5−x (SiMe3) x R3] (x = 1-3, R = Cl, Me) and their reactivity for propene polymerization is reported. The compounds 1-3 polymerize propene, albeit in a much lower activity than the reported [Ti(η5-C5Me5Me3]/B(C6F5)3 catalyst. Unlike the reported [Ti(η5-C5Me5Me3]/B(C6F5)3 catalyst, the quasi living polymerization was not observed. Instead, we observe rather unusual temperature effects when the trityl salt [Ph3C][B(C6F5)4] was used as activator. The activity increases with increasing temperature, whereas when B(C6F5)3 is used a decrease is observed The rather broad (>2) PDI indicates multisite catalysts, and 13C-NMR indicates predominantly atactic polypropene. The solid state structure of the hydrolysis product [{Ti(η5-C5H4(SiMe3)Cl2}O] (4) was determined.

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