The synthesis of tris(n-al1yl)uranium halides (2a-c) and their behaviour in the stereospecific polymerization of butadiene are reported. Independently from the nature of the halogen bound to uranium, very high 1,4-cis-polymer with a fairly good yield is obtained. The catalytic activity of allyluranium derivatives is very much improved when a Lewis acid is added as a co-catalyst. It is characteristic of the polymer to show a cis-content up to 99 % and an exceptionally high chain regularity at least for long chain sequencies. ZUSAMMENFASSUNG : stereospezifischen Polymerisation des Butadiens werden beschrieben. guten Ausbeuten unabhangig von der Art der Halogen-Uranverbindung erhalten. Cokatalysatoren gesteigert. auf, zumindest fur lange Ketten. Die Darstellung von Tris(n-al1yl)uranhalogeniden (2n-c) und ihre Wirkung bei der Polybutadiene mit sehr hohem 1,4-cis-Gehalt werden mit diesen Uranverbindungen in Die katalytische Wirkung der Allyluranverbindungen wird durch Lewissauren als Das Polymere weist bei hoher Kettenregelmaoigkeit einen 1,4-cis-Gehalt bis zu 99%
268ChemInform Abstract The complexes (IV) are prepared as shown in the scheme and are isolated as mono-dioxane solvates in 50-90% yield. All derivatives are thermally stable but are oxygen-and moisture-sensitive; they burn in air and must be handled and stored under nitrogen. The proton chemical shifts for the complexes are discussed.
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