Synthesis and characterization of new polynuclear titanium(IV) oxoalkyls: [Cp*TiR(mu-O)]3 and [Cp*Ti(mu-O)]3ClR2. Thermolysis of [Cp*TiEt(mu-O)]3 and the crystal structure of the first (mu3-ethylidyne)titanium complex [Cp*Ti(mu-O)]3(mu3-CMe).
The oxo trimer [Cp*TiCl(m-O)]3 (1) (Cp* = h5-C5Me5) reacts with organolithium LiR (R = Me, Ph, p-MeC6H4, CCPh) or Grignard reagents ClMgR (R = Me, Et, Pr, CH2Ph, CCH) to give the new alkyl oxo trimers [Cp*TiR(m-O)]3 (2-9) and [Cp*Ti(m-0)]3ClR2 (10-12) in good yield. In the case of [Cp*TiE3(m-0)]3 (6...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 1994 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/63025 |
| Acceso en línea: | http://hdl.handle.net/10017/63025 https://dx.doi.org/10.1021/om00018a007 |
| Access Level: | acceso abierto |
| Palabra clave: | Química Chemistry |
| Sumario: | The oxo trimer [Cp*TiCl(m-O)]3 (1) (Cp* = h5-C5Me5) reacts with organolithium LiR (R = Me, Ph, p-MeC6H4, CCPh) or Grignard reagents ClMgR (R = Me, Et, Pr, CH2Ph, CCH) to give the new alkyl oxo trimers [Cp*TiR(m-O)]3 (2-9) and [Cp*Ti(m-0)]3ClR2 (10-12) in good yield. In the case of [Cp*TiE3(m-0)]3 (6), the thermal decomposition at temperatures in the range of 195-200 OC leads to the preparation of the first example of a do (m3-alkylidyne) complex, [Cp*Ti(m-0)]3(m3-CMe) (13). The structure of this complex has been proved unequivocally by X-ray diffraction studies (space group Pnma, a = 12.104(6) A, b= 19.404(5) A, c = 13.744(1) A, Z = 4, R = 0.046, and Rw = 0.050). The oxo cluster core of 13 can be described like a six membered rhg, Ti303, where the three titanium atoms form an almost perfect equilateral triangle capped by a m3-ethylidyne ligand, with short nonbonded Ti···Ti contacts (average value of 2.82 A). |
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