Abstract
The hydroalumination of the allyl ethers CH2CHCH2OR with iBu2AlH yields the (3-alkoxypropyl)diisobutylaluminum complexes iBu2Al(CH2)3OR (R = Me (1), Et (2), Bu (3)). Et2AlCl and iBu2AlCl react with (2-(methoxymethyl)phenyl)lithium and (2-methoxybenzyl)magnesium chloride, yielding (2-(methoxymethyl)phenyl)diethylaluminum (4), (2-(methoxymethyl)phenyl)diisobutylaluminum (5), and (2-methoxybenzyl)diisobutylaluminum (7), respectively. The reaction of iBu2AlCl with (2-methoxyphenyl)lithium affords the dimeric bis((2-methoxyphenyl)diisobutylaluminum) (6). Et2AlCl and (8-ethoxynaphthyl)lithium form (8-ethoxynaphthyl)diethylaluminum (10) along with a few crystals of bis(8-ethoxynaphthyl)aluminum chloride (13). AlCl3 reacts with 2 equiv of (2-methoxybenzyl)magnesium chloride, yielding bis(2-methoxybenzyl)aluminum chloride (9). Ligand redistribution followed by metathesis was observed for the reactions of Me2AlCl and Et2AlCl with (2-methoxybenzyl)magnesium and (8-methoxynaphthyl)lithium, yielding bis(2-methoxybenzyl)methylaluminum (8), bis(8-methoxynaphthyl)methylaluminum (11), and bis(8-methoxynaphthyl)ethylaluminum (12), respectively. The new compounds have been characterized by elemental analysis, NMR spectroscopy, and mass spectrometry. The solid-state structures of 6, 8, 9, and 11−13 were determined by single-crystal X-ray diffraction. The new aluminum alkyls are very active cocatalysts in the TiCl4-catalyzed ethylene polymerization. 7 and 10 cause a higher productivity compared to the common cocatalyst Al2Et6. The activity depends strongly on the structure of the oxygen-stabilized aluminum alkyls and is also influenced by the Al/Ti ratio.
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