The family of hafnium-pyridylamido catalysts is industrially important for the homogeneous polymerization of olefins. This work will show how a collaborative effort between theory and experiment helped to uncover key steps in the polymerization process. Two of the key features described will be catalyst activation and the ability of this family to produce isotactic poly-α-olefins. The catalyst activation step is complicated by modification of the ligand by the monomer which potentially creates more than one active catalyst. The initial Hf-aryl bond of the pre-catalyst is modified by the insertion of one olefin. This monomer modification creates a new chiral center near the metal. It is believed the C1-symmetric catalyst inserts olefins only on one face leading to isotactic polypropylene.

Olefin polymerization with hafnium-pyridylamido catalysts

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