Reactivity of C-1-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 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], [...

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Published inChemistry : a European journal Vol. 25; no. 44; pp. 10478 - 10489
Main Authors Kulyabin, Pavel S., Goryunov, Georgy P., Mladentsev, Dmitry Y., Uborsky, Dmitry, Voskoboynikov, Alexander Z., Canich, Jo Ann M., Hagadorn, John R.
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 06.08.2019
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
polymerization
ACTIVATION
ZIRCONIUM
MECHANISM
BEHAVIOR
BONDS
heteroarylamides
insertion
CRYSTAL
TITANIUM
catalyst design
hafnium
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Summary: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.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201901899