Reactivity of C1-symmetric Heteroarylamido Hafnium Complexes towards Unsaturated Electrophilic Molecules: Development of New Families of Olefin Polymerization Catalysts.
P. S. Kulyabin, Georgy P. Goryunov, Dmitry Y. Mladentsev
Aug 6, 2019
Citations
5
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Journal
Chemistry
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Semantic Scholar
Key Takeaway Key Takeaway: C1-symmetric heteroarylamido hafnium complexes with unknown ligands can be modified to form active catalysts for olefin polymerization, offering a new, easy, and high-throughput approach for precatalyst modification.
Abstract
Heteroarylamido hafnium post-metallocenes with [C,N,N] ligands were functionalized via insertion of small electrophilic unsaturated molecules into CAr-Hf bond of the ligand, giving 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 formation of two diastereomers 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. Thus, a new approach to the feasible and easy "last 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.