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Cis- and trans-titanium complexes with doubly silyl-bridged dicyclopentadienyl ligands: molecular structure of [(TiCl)2(μ-O){(SiMe2)2(η-C5H3)2}]2(μ-O)2 |
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| Authors: | A M Cano J Cano T Cuenca P Gmez-Sal A Manzanero P Royo |
| Institution: | Departamento de Química Inorgánica, Universidad de Alcalá de Henares, Campus Universitario, Edificio Farmacia, E-28871, Alcalá de Henares, Spain |
| Abstract: | The reaction of TiCl4 with Li2(SiMe2)2(η5-C5H3)2] in toluene at room temperature afforded a mixture of cis- and trans-(TiCl3)2{(SiMe2)2(η5-C5H3)2}] in a molar ratio of 1/2 after recrystallization. The complex trans-(TiCl3)2{(SiMe2)2(η5-C5H3)2}] was hydrolyzed immediately by the addition of water to THF solutions to give trans-(TiCl2)2(μ-O){(SiMe2)2(η5-C5H3)2}] as a solid insoluble in all organic solvents, whereas hydrolysis of cis-(TiCl3)2{(SiMe2)2(η5-C5H3)2}] under different conditions led to the dinuclear μ-oxo complex cis-(TiCl2)2)(μ-O){(SiMe2)2(η5-C5H3)2}] and two oxo complexes of the same stoichiometry (TiCl)2(μ-O){(SiMe2)2(η5-C5H3)2}]2(μ-O)2 as crystalline solids. Alkylation of cis- and trans-(TiCl3)2{(SiMe2)2(η5-C5H3)2}] with MgCIMe led respectively to the partially alkylated cis-(TiMe2Cl)2{(SiMe2)2(η5-C5H3)2}] and the totally alkylated trans-(TiMe3)2{(SiMe2)2(η5-C5H3)2}] compounds. The crystal and molecular structure of the tetranuclear oxo complex (TiCl)2(μ-O){(SiMe2)2(η5-C5H3)2}]2(μ-O)2 was determined by X-ray diffraction. |
| Keywords: | Crystal structures Titanium complexes Silyl-bridged cyclopentadienyl complexes |
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