Complete Defluorination of 1,2,3,4-Tetramethyl-5-(trifluoromethyl)cyclopentadienide by titaniumtetrakisdimethylamide. Selective Formation of a Cyclic Hexanuclear Titaniumfluoroamide and 6,6-Dimethylaminotetramethylfulvene
1,2,3,4-Tetramethyl-5-(trifluoromethyl)cyclopentadiene (Cp*CF3-H, 1) reacts with [Ti(NMe2)4] (2) under mild conditions to give [Ti(m-NMe2)(NMe2)(m-F)(F)]6 (3) in nearly quantitative yield. The molecular structure of 3 consists of a ring of six [TiF2(NMe2)2] edge-bridged octahedra. Titanium complexes...
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2001 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/63508 |
| Acceso en línea: | http://hdl.handle.net/10017/63508 https://dx.doi.org/10.1002/1521-3765(20010202)7:33.0.CO;2-1 |
| Access Level: | acceso abierto |
| Palabra clave: | Amides C-F Bond activation Fluorine Titanium Química Chemistry |
| Sumario: | 1,2,3,4-Tetramethyl-5-(trifluoromethyl)cyclopentadiene (Cp*CF3-H, 1) reacts with [Ti(NMe2)4] (2) under mild conditions to give [Ti(m-NMe2)(NMe2)(m-F)(F)]6 (3) in nearly quantitative yield. The molecular structure of 3 consists of a ring of six [TiF2(NMe2)2] edge-bridged octahedra. Titanium complexes containing the Cp*CF3 ligand, which was the primary intention of these investigations, were not observed. C5Me4=C(NMe2)2 (4) was isolated as a by-product. The complete defluorination of an aliphatic CF3 group occurs during the reaction. The reaction mechanism involves the primary formation of a difluorofulvene intermediate C5Me4=CF2 (5), which was monitored by NMR studies. Density functional theory calculations predict a highly charged C6 atom (+0.87) in 5, which is discussed as the driving force of the reaction. |
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