Reactivity of μ3-alkylidyne groups on an organotitanium oxide:: Insertion of isocyanides and carbon monoxide into the complexes [{TiCp*(μ-O)}3(μ3-CR)] (R = H, Me)
tert-Butyl isocyanide reacts with the m3-alkylidyne complex [{TiCp*(m-O)}3(m3-CH)] (1, Cp* = h5- C5Me5) to give a single insertion into a m3-carbon ± titanium bond and the formation of the new derivative [{TiCp* (m-O)}3(m3-h2-HCCNtBu)] (3). Similar reactions of 2,6-Me2C6H3NC and 2,4,6- Me3C6H2NC wit...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 1998 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/63083 |
| Acceso en línea: | http://hdl.handle.net/10017/63083 https://dx.doi.org/10.1002/(SICI)1521-3765(19980710)4:73.0.CO;2-4 |
| Access Level: | acceso abierto |
| Palabra clave: | Alkylidyne complexes Cyclopentadienes Insertions Structure elucidation Titanium Química Chemistry |
| Sumario: | tert-Butyl isocyanide reacts with the m3-alkylidyne complex [{TiCp*(m-O)}3(m3-CH)] (1, Cp* = h5- C5Me5) to give a single insertion into a m3-carbon ± titanium bond and the formation of the new derivative [{TiCp* (m-O)}3(m3-h2-HCCNtBu)] (3). Similar reactions of 2,6-Me2C6H3NC and 2,4,6- Me3C6H2NC with the complexes [{TiCp*(m-O)}3(m3-CR)] (R = H (1), Me (2)) in a 1:2 molar ratio at room temperature lead to the double insertion compounds [{TiCp*(m-O)}3{m3-h4-RC(CNAr)2}] (R = H, Ar = 2,6-Me2C6H3 (6), 2,4,6-Me3C6H2 (7); R = Me, Ar = 2,6-Me2C6H3 (8), 2,4,6-Me3C6H2 (9)). Curiously, when the reactions with 2,6- Me2C6H3NC are carried out in a 1:1 molar ratio, diinsertion products 6 or 8, and unchanged m3-alkylidyne complex 1 or 2, respectively, are detected. From the mixture of 6 and 1 the monoinsertion product [{TiCp*(m-O)}3{m3-h2-HCCN(2,6-Me2C6H3)}] (10) is formed slowly at room temperature. However, it is necessary to heat the mixture of 8 and 2 at 130 8C for five days to observe some evolution; this finally leads to the zwitterionic compound [{TiCp*(m-O)}3{m3-h2-CC(Me)N(2,6-Me2C6H3)}] (11). Complex 1 also reacts with excess carbon monoxide at room temperature to produce only compound [{TiCp*(m- O)}3]2(m6-L)] (L = C6H2O4) (5), in which the organic ligand L connects two Ti3O3 cores. The molecular structures of complexes 9 and 11 have been determined by X-ray diffraction analyses. |
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