Preparation of Half- and Post-Metallocene Hafnium Complexes with Tetrahydroquinoline and Tetrahydrophenanthroline...

Hafnium complexes have drawn attention for their application as post-metallocene catalysts with unique performance in olefin polymerization. In this work, a series of half-metallocene HfMe₂ complexes, bearing a tetrahydroquinoline framework, as well as a series of [N^amido,N,C^aryl]HfMe₂-type post-metallocene complexes, bearing a tetrahydrophenanthroline framework, were prepared; the structures of the prepared Hf complexes were unambiguously confirmed by X-ray crystallography. When the prepared complexes were reacted with anhydrous [(C₁₈H₃₇)₂N(H)Me]⁺[B(C₆F₅)₄]^-, desired ion-pair complexes, in which (C₁₈H₃₇)₂NMe coordinated to the Hf center, were cleanly afforded. The activated complexes generated from the half-metallocene complexes were inactive for the copolymerization of ethylene/propylene, while those generated from post-metallocene complexes were active. Complex bearing bulky isopropyl substituents (12) exhibited the highest activity. However, the activity was approximately half that of the prototype pyridylamido-Hf Dow catalyst. The comonomer incorporation capability was also inferior to that of the pyridylamido-Hf Dow catalyst. However, 12 performed well in the coordinative chain transfer polymerization performed in the presence of (octyl)₂Zn, converting all the fed (octyl)₂Zn to (polyolefinyl)₂Zn with controlled lengths of the polyolefinyl chain.