Diamido Complexes of Titanium and Zirconium as Catalyst Precursors for Ethylene Polymerization

A series of 8 new complexes of titanium and zirconium with diamido ligands bearing an ethylene and propylene bridge between the two amido groups were synthesized and tested for ethylene polymerization. Titanium complexes bearing an ethylene bridge between the two amido groups showed higher activities than the derivatives with a propylene bridge. In the case of the zirconium complexes, the propylene bridged complexes were more active than the corresponding ethylene bridged. The introduction of bulky groups on the ligand structure resulted in an increase in the activity. DFT calculations were performed to determine the activation energy barriers for different reaction steps. The calculated activation energy for the insertion of ethylene into an M-CH3 bond is in the range of 12.2-16.8 kcal/mol and the activation energy for the chain termination via β-H transfer reaction is 12.5-14.4 kcal/mol.