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• W2109452823 abstract "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, i Pr, t Bu, 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) Å for 1 PhCl2 , 2 PhCl , and 3 Ph , respectively. All four alkyl/aryl series with Me, i Pr, t Bu, 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 °C. The phenyl series showed much higher catalytic activity, which ranged from 43.2 and 65.4 kg (mmol of Ti⋅h) −1 , than the Me, i Pr, and t Bu series (19.2 and 36.6 kg (mmol of Ti⋅h) −1 ). Among the phenyl series, the bis(phenoxide) complex of 2 PhCl showed the highest activity of 65.4 kg (mmol of Ti⋅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." @default.
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• W2109452823 date "2010-05-07" @default.
• W2109452823 modified "2023-10-18" @default.
• W2109452823 title "Sterically Less-Hindered Half-Titanocene(IV) Phenoxides: Ancillary-Ligand Effect on Mono-, Bis-, and Tris(2-Alkyl-/arylphenoxy) Titanium(IV) Chloride Complexes" @default.
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• W2109452823 doi "https://doi.org/10.1002/chem.201000191" @default.
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