Metallocenes synthesis

Togni, A., Halterman, R. L. (Eds.), Metallocenes Synthesis, Reactivity, Applications, Wiley-VCH, Weinheim, 1998, Vols. 1 and 2 and references therein. 

Bis (indenyl) complexes, with Zr(IV), 4, 935 Bis(indenyl)dimethyl metallocenes, synthesis, 4, 884-885 Bis(indenyl)zirconium sandwich complexes, preparation and reactivity, 4, 728... 

Even non-conjugated di-olefins may be used in these systems as precursors for the (conjugated diene)metallocene synthesis. They become isomerized under the reaction conditions at the bent metallocene system.81 Even vinylcyclopropanes yield the corresponding (l,3-diene)metallocene complexes when treated with the reagent 71. The three-membered ring is readily opened under the typical reaction conditions.82... 

Looking at the preparation of supported metallocenes, synthesis of the metallocene on the carrier is found as well as fixing a metallocene either via functionality at the ligand or by direct reaction with the carrier, in both cases followed by activation with MAO or trialkylaluminium, but more common is heterogenization of the cocatalyst prior to mixing the modified carrier with the metallocene and activation by trialkylaluminium. 

A. Togni in New Chiral Ferrocenyl Ligands for Asymmetric Catalysis in Metallocenes. Synthesis, Reactivity, Applications , eds. A. Togni and R. L. Halterman, Weinheim, 1998, Vol. 2, p. 685. 

The reaction is smooth in ether-benzene solvent with a tenfold excess of the organolithium compound. In this reaction complete decomposition of nickelocene and formation of Ni + is not excluded further reaction in the ordinary manner of metallocene synthesis to give the final reaction product could then occur. 

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