Non-traditional Ziegler-Natta catalysis in α-olefin transformations: Reaction mechanisms and product design

This paper describes our recent results in the field of zirconocene-catalyzed α-oltfin transformations, and focuses on questions regarding the reaction mechanism, rational design of zirconocene pre-catalysts, as well as prospective uses of α-olefin products. It has been determined that a wide range of α-olefin-based products, namely vinylidene dimers, oligomers and polymers, can be prepared via catalysis by zirconocene dichlorides, activated by a minimal (10–20 eq.) amount of MAO. We assumed that in the presence of minimal quantities of MAO, various types of zirconocene catalysts form different types of catalytic particles. In the case of bis-cyclopentadienyl complexes, the reactive center is formed under the influence of R₂AlCl, which makes the chain termination via β-hydride elimination significantly easier, with α-olefin dimers being formed as the primary product. Bis-indenyl complexes and their heteroanalogues, form stable cationic catalytic particles and effectively catalyze the polymerization. Mono-indenyl and mono-substituted bis-cyclopentadienyl-ansa complexes catalyze α-olefin oligomerization. Effective catalysts of dimerization, oligomerization and polymerization of α-olefins in the presence of minimal MAO quantities are proposed. Prospects of using α-olefin dimers, oligomers and polymers in the synthesis of branched hydrocarbon functional derivatives (dimers), high quality, low viscosity motor oils (oligomers), and thickeners and absorbents (polymers) are examined.