The development of new metallocene-based polymerization catalysts and innovative processes derived thereof still constitutes a challenge for the manufacturing of polyolefinic materials with tailored properties (e. g. particular microstructure or topology, ultra-high molecular weight, high melting transition, and their combinations) for contemporary commercial applications. This personal account summarizes our continuing endeavors to advance the family of industry-relevant stereoselective propylene polymerization catalysts based on C -symmetric group 4 ansa-metallocenes incorporating multi-substituted fluorenyl-cyclopentadienyl {Cp/Flu} ligands. Within the framework of this project, valuable structural and catalytic data, harvested both for neutral metallocenes and for metallocenium ion-pairs, have been used for rational design of more efficient catalytic systems, reluctant towards side reactions, and for providing new stereoregular value-added polymer materials.
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