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New approaches to nitrogen ligands bearing electron withdrawing groups and their role in coordination chemistry
The search for non-cyclopentadienide-type catalyst systems continues,
driven by industry’s desire to obtain even greater control over polymer properties
and extend the family of products to include new monomer combinations. At the
forefront of this search are two ligand types, diketimines and their oxygensubstituted analogs, the aminoenones. We have recently found an efficient and
clean synthetic pathway, developed in conjunction with the Los Alamos National
Laboratory, to these ligand types, utilizing novel aluminum chemistry. A variety
of dimeric alkylaminoalanes, with the general formula, [Me2AlN(H)Arf]2, that
feature aryl groups with varying degrees of fluorination, are presented. A nonfluorinated pyridine derivative that resulted in a novel pentasubstituted aluminum
species is also discussed. The use of these new aminoalane reagents for the
transformation of the ketone functionality to the imine functionality was very
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successful, and in most instances, led to a higher yield of a cleaner product, than
with the traditional methodology. Finally, the coordination capability of this class
of ligand was studied by the reactions with both early and late transition metals,
as well as the main group metal aluminum. Simple adducts of titanium,
vanadium, chromium, and platinum were prepared, as well as complexes of
titanium, zirconium, and aluminumChemistr