Bis(1,3-di-tert-butylimidazolin-2-iminato) Titanium Complexes as Effective Catalysts for the Monodisperse Polymerization of Propylene

The use of bis­(1,3-di-tert-butylimidazolin-2-iminato) titanium dichloride (1) and dimethyl (2) complexes in the polymerization of propylene is presented. The complexes were activated using different amounts of methylalumoxane (MAO), giving in each case a very active catalytic mixture and producing polymers with a narrow molecular weight distribution (polydispersity = 1.10). The use of the cocatalyst triphenylcarbenium (trityl) tetra­(pentafluorophenyl)­borate totally inhibits the reaction, producing the corresponding bis­(1,3-di-tert-butylimidazolin-2-iminato) titanium­(III) methyl complex, the trityl radical (•CPh3), the anionic MeB­(C6F5)4–, B­(C6F5)3, and the bis­(1,3-di-tert-butylimidazolin-2-iminato) titanium­(IV) dimethyl·B­(C6F5)3 complex. The use of a combination of physical methods such as NMR, ESR-C60, and MALDI-TOF analyses enabled us to propose a plausible mechanism for the polymerization of propylene, presenting that the polymerization is mainly carried out in a living fashion. In addition, we present a slow equilibrium toward a small amount of a dormant species responsible for 2,1-misinsertions and chain transfer processes.