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

uitably activated, (Cp*){N(tBu)C(Me)N(Et)}ZrMe 2 is known to initiate the 'living' and isotacticselective 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 MAOactivated 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.