Synthesis and characterization of titanium(IV) complexes containing the diphenylphosphino- and diphenylthiophosphoryl-functionalized cyclopentadienyl ligand. Crystal and molecular structure of Ti(η5-C5H4PPh2)Cl3
The trimethylsilyl cyclopentadiene derivative C5H4(SiMe3)PPh2 (1) was treated with TiCl4 to give the air- and moisture-sensitive mono(cyclopentadienyl) compound Ti(η5-C5H4PPh2)Cl3 (4). Reaction of 4 with Mg(CH2C6H5)2(THF)2 gave Ti(η5-C5H4PPh2)(CH2C6H5)3 (5). Reactions of the lithium and thallium der...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2000 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/4211 |
| Acceso en línea: | http://hdl.handle.net/10017/4211 https://dx.doi.org/10.1016/S0022-328X(99)00414-3 |
| Access Level: | acceso abierto |
| Palabra clave: | Cyclopentadienyl ligand Phosphorus Ligand redistribution Titanium Ciencia Química inorgánica Science Chemistry, inorganic |
| Sumario: | The trimethylsilyl cyclopentadiene derivative C5H4(SiMe3)PPh2 (1) was treated with TiCl4 to give the air- and moisture-sensitive mono(cyclopentadienyl) compound Ti(η5-C5H4PPh2)Cl3 (4). Reaction of 4 with Mg(CH2C6H5)2(THF)2 gave Ti(η5-C5H4PPh2)(CH2C6H5)3 (5). Reactions of the lithium and thallium derivatives M{C5H4P(S)Ph2} (M=Li (2), Tl (3)) with one equiv. of TiCl4 afforded the mono(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}Cl3 (6), whereas reaction with 0.5 equiv. of TiCl4 gave the bis(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}2Cl2 (8). Compound 6 was also isolated as a minor product from the reaction of Ti{η5-C5H4P(S)Ph2}2Cl2 (8) with one equiv. of TiCl4. The major product was identified as an inseparable mixture of two compounds [Ti{η5-C5H4P(S)Ph2}2Cl2·TiCl4]n (7a and 7b). Reaction of Ti(η5-C5H5)Cl3 with 3 afforded the ‘mixed-ring’ bis(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}(η5-C5H5)Cl2 (9). Compounds 6–9 are very moisture-sensitive and easily decompose to form the cyclopentadiene C5H5P(S)Ph2. Structural data of these complexes indicate η5-coordination of the substituted cyclopentadienyl ligands and this coordination mode was confirmed by X-ray crystal structure analysis of compound 4. |
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