om4001555_si_002.cif (90.77 kB)
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 2013-05-13, 00:00 authored by Ilya E. Nifant’ev, Pavel V. Ivchenko, Vladimir V. Bagrov, Sandor M. Nagy, Shahram Mihan, Linda N. Winslow, Andrei V. ChurakovA 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
typeZr complexes where the aromatic system of the precursor
remains intactcan 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.
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4 molDistinct Coordination ModesEthylene Polymerization CatalysisA seriespolymerization catalystsTridentate LigandMAOgroup 4 tetrabenzyl complexes MBn 4 resultspolyethylene copolymersmultimodal MWDsbiZrCl 4.amine complexesbenzyl substitutionligand precursorsamide complexescomplexes resultGroup 4 Metal Alkyls Resultingazine fragment
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