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Synthesis and Reactivity of Trimethylsilyl Substituted Mono(cyclopentadienyl)titanium Alkyl Complexes

Sassmannshausen, J; Baumgartner, J; (2009) Synthesis and Reactivity of Trimethylsilyl Substituted Mono(cyclopentadienyl)titanium Alkyl Complexes. KINET CATAL+ , 50 (5) 676 - 683. 10.1134/S0023158409050097.

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Abstract

The preparation of a series of titanium half-sandwich compounds [Ti(eta(5)-C5H5-x(SiMe3)(x)R-3] (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(eta(5)-C5Me5Me3]/B(C6F5)(3) catalyst. Unlike the reported [Ti(eta(5)-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 C-13-NMR indicates predominantly atactic polypropene. The solid state structure of the hydrolysis product [{Ti(eta(5)-C5H4(SiMe3)Cl-2}O] (4) was determined.

Type:Article
Title:Synthesis and Reactivity of Trimethylsilyl Substituted Mono(cyclopentadienyl)titanium Alkyl Complexes
DOI:10.1134/S0023158409050097
Keywords:OLEFIN POLYMERIZATION CATALYSTS, CATIONIC ZIRCONOCENE COMPLEXES, HALF-SANDWICH COMPLEXES, METALLOCENIUM ION-PAIRS, CRYSTAL-STRUCTURE, ACTIVATION PROCESSES, PHENYL COORDINATION, BENZYL COMPOUNDS, ARENE COMPLEXES, BOND ACTIVATION
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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