Alk‐1‐ene Polymerization in the Presence of a Monocyclopentadienyl Zirconium( IV ) Acetamidinate Catalyst: Microstructural and Mechanistic Insights

Suitably activated, (Cp*){N(tBu)C(Me)N(Et)}ZrMe2 is known to initiate the ‘living’ and isotactic‐selective polymerization of alk‐1‐enes, and it can be used to synthesize block copolymers and stereoblock polymers. We report a full molecular kinetic investigation of propene, but‐1‐ene, and hex‐1‐ene polymerization with a MAO‐activated catalyst system. By combining NMR microstructural polymer analysis with QM modeling of the active species, the complicated regio‐ and stereochemistry of the polyinsertion process, as well as the active chain‐transfer pathways, are investigated. The perspectives and limitations of this catalyst for application in (stereo)block polymerizations are discussed. magnified image