title: Sterically less-hindered half-titanocene(IV) phenoxides: ancillary-ligand effect on mono-, bis-, and tris(2-alkyl-/arylphenoxy) titanium(IV) chloride complexes.
abstract: A series of mono-, bis-, and tris(phenoxy)-titanium(IV) chlorides of the type [Cp*Ti(2-R-PhO)(n)Cl(3-n)] (n=1-3; Cp*=pentamethylcyclopentadienyl) was prepared, in which R=Me, iPr, tBu, and Ph. The formation of each mono-, bis-, and tris(2-alkyl-/arylphenoxy) series was authenticated by structural studies on representative examples of the phenyl series including [Cp*Ti(2-Ph-PhO)Cl(2)] (1 PhCl2), [Cp*Ti(2-Ph-PhO)(2)Cl] (2 PhCl), and [Cp*Ti(2-Ph-PhO)(3)] (3 Ph). The metal-coordination geometry of each compound is best described as pseudotetrahedral with the Cp* ring and the 2-Ph-PhO and chloride ligands occupying three leg positions in a piano-stool geometry. The mean Ti-O distances, observed with an increasing number of 2-Ph-PhO groups, are 1.784(3), 1.802(4), and 1.799(3) A for 1 PhCl2, 2 PhCl, and 3 Ph, respectively. All four alkyl/aryl series with Me, iPr, tBu, and Ph substituents were tested for ethylene homopolymerization after activation with Ph(3)C(+)[B(C(6)F(5))(4)](-) and modified methyaluminoxane (7% aluminum in isopar E; mMAO-7) at 140 degrees C. The phenyl series showed much higher catalytic activity, which ranged from 43.2 and 65.4 kg (mmol of Ti x h)(-1), than the Me, iPr, and tBu series (19.2 and 36.6 kg (mmol of Ti x h)(-1)). Among the phenyl series, the bis(phenoxide) complex of 2 PhCl showed the highest activity of 65.4 kg (mmol of Ti x h)(-1). Therefore, the catalyst precursors of the phenyl series were examined by treating them with a variety of alkylating reagents, such as trimethylaluminum (TMA), triisobutylaluminum (TIBA), and methylaluminoxane (MAO). In all cases, 2 PhCl produced the most catalytically active alkylated species, [Cp*Ti(2-Ph--PhO)MeCl]. This enhancement was further supported by DFT calculations based on the simplified model with TMA.
authors.affiliation: Department of Advanced Materials Chemistry, Sejong, Korea University, 208 Seochang, Chochiwon, Chung-nam 339-700, Korea.
authors.forename: Tae-Jin
authors.initials: TJ
authors.lastname: Kim
authors.forename: Sung-Kwan
authors.initials: SK
authors.lastname: Kim
authors.forename: Beom-Jun
authors.initials: BJ
authors.lastname: Kim
authors.forename: Ho-Jin
authors.initials: HJ
authors.lastname: Son
authors.forename: Jong Sok
authors.initials: JS
authors.lastname: Hahn
authors.forename: Minserk
authors.initials: M
authors.lastname: Cheong
authors.forename: Mariusz
authors.initials: M
authors.lastname: Mitoraj
authors.forename: Monika
authors.initials: M
authors.lastname: Srebro
authors.forename: Łukasz
authors.initials: Ł
authors.lastname: Piekoś
authors.forename: Artur
authors.initials: A
authors.lastname: Michalak
authors.forename: Sang Ook
authors.initials: SO
authors.lastname: Kang