Abstract
Phosphorous-bridged bisphenoxy titanium complexes were synthesized and their ethylene polymerization behavior was investigated. Bis[3- tert-butyl-5-methyl-2-phenoxy](phenyl)phosphine tetrahydrofuran titanium dichloride ( 4a) was obtained by treatment of 3 equiv of n-BuLi with bis[3- tert-butyl-2-hydroxy-5-methylphenyl](phenyl)phosphine hydrochloride salt ( 3a) followed by TiCl 4(THF) 2 in THF. THF-free complexes 5a– 5d were synthesized more conveniently by the direct reaction of MOM-protected ligands ( 2a– 2d) with TiCl 4 in toluene. X-ray analysis of 4a revealed that the ligand is bonded to the octahedral titanium (IV) center in a facial fashion and two chlorine atoms possess cis-geometry. Complexes 4a and 5a– 5d were utilized as catalyst precursors for ethylene polymerization. Complex 5c gave high molecular weight polyethylene ( M w = 1,170,000, M w/ M n = 2.0) upon activation with Al( i Bu) 3/[Ph 3C][B(C 6F 5) 4] (TB). Ethylene polymerization activity of 5d activated with Al( i Bu) 3/TB reached 49.0 × 10 6 g mol (cat) −1 h −1.
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