Reactivity of C1 -Symmetric Heteroarylamido Hafnium Complexes towards Unsaturated Electrophilic Molecules: Development of New Families of Olefin Polymerization Catalysts.

Heteroarylamido hafnium post-metallocenes with [C,N,N] ligands were functionalized by the insertion of small electrophilic unsaturated molecules into the CAr -Hf bond of the ligand, which gave rise to various 1,1- and 1,2-insertion complexes with the modified ligands of previously unknown [O,N,N], [N,N,N], [O,N,N,N], and [N,N,N,N] types. It was found that C1 symmetry of the starting complexes, in some cases, results in the formation of two diastereoisomers after 1,1- or 1,2-insertion. Most of the obtained novel complexes were shown to form active catalysts for olefin polymerization in the presence of MAO (methylaluminoxane). Thus, a new approach to the feasible and easy "late stage" modification of the precatalyst structure has been suggested; it can be performed immediately prior to the polymerization tests without isolation and even in a high-throughput manner.