An Efficient Titanium Amidinate Catalyzed Version of Ziegler's "Aufbaureaktion"

Diethylamidotitanium trichloride reacts with a variety of bulky amidines ArN(H)C(Ar′)NAr [Ar = 2,6‐diisopropylphenyl; Ar′ = Ph, p‐Me2NC6H4, p‐MeOC6H4, p‐(2,5‐dimethylpyrrole)C6H4] to form ammonium titanates. These new titanium complexes undergo polyethylenyl chain transfer polymerization to aluminium alkyls after activation with d‐MAO (“dry methylaluminoxane”). Ethylene is polymerized with an activity of up to 1000 kgPE molcat–1 h–1 bar–1 in the presence of 1000 equiv. of triethylaluminium. Linear aluminium‐terminated polyethylene is the only product observed. This polymerization process can be viewed as an efficient catalytic version of Ziegler's “Aufbaureaktion”. New ammonium titanates undergo polyethylenyl chain transfer polymerization to triethylaluminium after activation with d‐MAO (“dry methylaluminoxane”). Polymerization activities of up to 1000 kgPE molcat–1 h–1 bar–1 in the presence of 1000 equiv. of triethylaluminium were observed. Linear aluminium‐terminated polyethylene is found. This polymerization process can be viewed as an efficient version of Ziegler's “Aufbaureaktion”.