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Reaction of 2,8-Bis(o‑hydroxyaryl)quinolines with Group 4 Metal Alkyls Resulting in Three Distinct Coordination Modes of the Tridentate Ligand. X‑ray Structure of Complexes and Performance as Precursors in Ethylene Polymerization Catalysis

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posted on 13.05.2013, 00:00 by Ilya E. Nifant’ev, Pavel V. Ivchenko, Vladimir V. Bagrov, Sandor M. Nagy, Shahram Mihan, Linda N. Winslow, Andrei V. Churakov
A series of bis­(o-hydroxyphenyl)­quinolines have been prepared, starting from 2,8-dibromoquinoline. Reaction of these new ligand precursors with group 4 tetrabenzyl complexes MBn4 results in benzyl substitution of the azine fragment with the formation of amide complexes (M = Ti) or amine complexes with an N–H fragment coordinated to the metal (M = Zr, Hf). The third structural typeZr complexes where the aromatic system of the precursor remains intactcan be prepared through the reaction of the bis­(o-hydroxyphenyl)­quinolones with 4 mol of methyllithium, followed by ZrCl4. The new complexes result in active polymerization catalysts when activated with MAO/borate cocatalysts on silica supports, resulting in polyethylene copolymers with very high molecular weights and multimodal MWDs.