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Reactivity of C 1 ‐Symmetric Heteroarylamido Hafnium Complexes towards Unsaturated Electrophilic Molecules: Development of New Families of Olefin Polymerization Catalysts
Author(s) -
Kulyabin Pavel S.,
Goryunov Georgy P.,
Mladentsev Dmitry Y.,
Uborsky Dmitry V.,
Voskoboynikov Alexander Z.,
Canich Jo Ann M.,
Hagadorn John R.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901899
Subject(s) - methylaluminoxane , electrophile , diastereomer , polymerization , chemistry , reactivity (psychology) , ligand (biochemistry) , catalysis , olefin fiber , hafnium , medicinal chemistry , molecule , polymer chemistry , stereochemistry , zirconium , metallocene , organic chemistry , polymer , medicine , biochemistry , alternative medicine , receptor , pathology
Heteroarylamido hafnium post‐metallocenes with [C,N,N] ligands were functionalized by the insertion of small electrophilic unsaturated molecules into the C Ar −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 C 1 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.