ABSTRACT
A series of zirconocenes L2ZrCl2 (23 examples) were studied as catalysts in the reaction of alkenes with AlEt3. The catalyst activity and reaction chemoselectivity were found to depend on the ligand structure in the complex and the nature of the solvent. The alkyl exchange in the triethylaluminum dimer was studied by NMR spectroscopy; a solvent effect on the alkyl exchange parameters was established. In the reaction between L2ZrCl2 and AlEt3, the formation of intermediates L2ZrEtCl, L2Zr(µ-Cl)CH2CH2AlEt2, L2Zr(µ-H)CH2CH2AlEt2, and L2Zr(µ-Cl)CH2CH(AlEt2)2 was shown; the ratio of the intermediates depends on the ligand structure in the initial complex and the solvent. The exchange in the ethanediyl bridge ZrCH2CH2Al, proceeding via zirconocenecyclopropane structures, was demonstrated for the first time for five-membered bimetallic complexes L2Zr(µ-Cl)CH2CH2AlEt2 with ansa-ligands (L2 = Me2SiCp2, H2CInd2, Me2CInd2, Me2SiInd2, and C2H4Ind2). Five-membered bimetallic complexes were shown to participate in the formation of cyclic organoaluminum products - 3-substituted alumolanes.
