Regio- and stereochemistry of the first insertion step in the 1,3-butadiene polymerization catalyzed by CpTiCl3-MAO

In order to simulate an insertion of a conjugated diene on a σ chain, experimental and theoretical studies, relative to the first insertion step, are reported. Unexpectedly 56% of 1,2-primary and 44% of 4,1-trans first inserted units were obtained, by using as catalyst CpTiCl3/MAO/Al(13CH3)3. The experimental results were rationalized by DFT (Density Functional Theory) calculations, by including a solvent molecule coordinated to the catalytic site during the first insertion step.