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Fluorosilyl-Substituted Cyclopentadienyltitanium(IV) Complexes: Synthesis, Structure, and Styrene Polymerization Behavior

Rok: 2007

Druh publikace: článek v odborném periodiku

Název zdroje: Organometallics

Název nakladatele: American Chemical Society

Místo vydání: Washington

Strana od-do: 2735-2741

Tituly:

Jazyk	Název	Abstrakt	Klíčová slova
cze	Fluorosilyl-substitutované cyklopentadienyltitaničité komplexy: Příprava, struktura a jejich použití pro polymerace styrenu	The synthesis and characterization of new halo-silyl substituted titanium(IV) derivatives [TiCl3(h5-C5H4SiCl3)] (9), [TiCl3(h5-C5H4SiMe2F)] (10), [TiCl3(h5-C5H4SiMeF2)] (11), [TiCl3(h5-C5H4SiF3)] (12) and [TiF3(h5-C5H4SiMe2F)] (13) are reported. The reaction of lithiated trimethylsilylcyclopentadienide with Me2SiCl2, MeSiCl3 or SiCl4 gave chlorosilyl(trimethylsilyl)cyclopentadienes that were fluorinated with Me3SnF to yield fluorosilyl derivatives C5H4(SiMe2F)SiMe3 (4), C5H4(SiMeF2)SiMe3 (5) and C5H4(SiF3)SiMe3 (6), respectively. Addition of disilylated compounds 4 - 6 to a solution of TiCl4 gave the respective half-sandwich titanium complexes 10 - 12, which could be alternatively prepared by selective fluorination of the corresponding chlorosilyl-substituted cyclopentadienyltitanium(IV) trichlorides with Me3SnF. Completely fluorinated [TiF3(C5H4SiMe2F)] (13) was prepared from [TiCl3(C5H4SiMe2Cl)] (7) and four equivalents of Me3SnF. The molecular structures of the pentameric 13 and the monomeric 10 were determined by X-ray diffraction analysis. The 47,49Ti NMR and UV-Vis spectroscopy showed the electron-releasing nature of the SiMe2Cl, SiMe2F, SiMeCl2 and SiMeF2 substituents, whereas SiCl3 and SiF3 groups had electron-withdrawing properties. The catalytic behavior of these half-sandwich titanium compounds in styrene polymerization was studied in the presence of excess methylaluminoxane.	Titan, fluorosilylsubstituované cyklopentadieny, metalloceny, 47,49Ti NMR, RTG analýza, elektronová spektroskopie, polymerizace styrenu, katalýza
eng	Fluorosilyl-Substituted Cyclopentadienyltitanium(IV) Complexes: Synthesis, Structure, and Styrene Polymerization Behavior	The synthesis and characterization of new halo-silyl substituted titanium(IV) derivatives [TiCl3(h5-C5H4SiCl3)] (9), [TiCl3(h5-C5H4SiMe2F)] (10), [TiCl3(h5-C5H4SiMeF2)] (11), [TiCl3(h5-C5H4SiF3)] (12) and [TiF3(h5-C5H4SiMe2F)] (13) are reported. The reaction of lithiated trimethylsilylcyclopentadienide with Me2SiCl2, MeSiCl3 or SiCl4 gave chlorosilyl(trimethylsilyl)cyclopentadienes that were fluorinated with Me3SnF to yield fluorosilyl derivatives C5H4(SiMe2F)SiMe3 (4), C5H4(SiMeF2)SiMe3 (5) and C5H4(SiF3)SiMe3 (6), respectively. Addition of disilylated compounds 4 - 6 to a solution of TiCl4 gave the respective half-sandwich titanium complexes 10 - 12, which could be alternatively prepared by selective fluorination of the corresponding chlorosilyl-substituted cyclopentadienyltitanium(IV) trichlorides with Me3SnF. Completely fluorinated [TiF3(C5H4SiMe2F)] (13) was prepared from [TiCl3(C5H4SiMe2Cl)] (7) and four equivalents of Me3SnF. The molecular structures of the pentameric 13 and the monomeric 10 were determined by X-ray diffraction analysis. The 47,49Ti NMR and UV-Vis spectroscopy showed the electron-releasing nature of the SiMe2Cl, SiMe2F, SiMeCl2 and SiMeF2 substituents, whereas SiCl3 and SiF3 groups had electron-withdrawing properties. The catalytic behavior of these half-sandwich titanium compounds in styrene polymerization was studied in the presence of excess methylaluminoxane.	Titanium;Fluorosilyl substituted cyclopentadienes;Monocyclopentadienyl titanium compounds;47,49Ti NMR;X-ray structure;UV-Vis;Styrene polymerization

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