Transfer Hydrogenation Processes to μ3-Alkylidyne Groups on the Organotitanium Oxide [Ti3CpO3]
The photochemical treatment Of mu(3)-alkylidyne complexes [{TiCp*(mu-O)}(3)(mu(3)-CR)] (R = H (1), Me (2), Cp* = eta(5)-C5Me5) with the amines (2,6-Me2C6H3)NH2, Et2NH, and Ph2NH and the imine Ph2C=NH leads to the partial hydrogenation of the alkylidyne moiety that is supported on the organometallic...
| Autores: | , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2002 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/63173 |
| Acceso en línea: | http://hdl.handle.net/10017/63173 https://dx.doi.org/10.1002/1521-3765(20020215)8:43.0.CO;2-H |
| Access Level: | acceso abierto |
| Palabra clave: | Hydrogenation Nligands Oxo ligands Titanium Química Chemistry |
| Sumario: | The photochemical treatment Of mu(3)-alkylidyne complexes [{TiCp*(mu-O)}(3)(mu(3)-CR)] (R = H (1), Me (2), Cp* = eta(5)-C5Me5) with the amines (2,6-Me2C6H3)NH2, Et2NH, and Ph2NH and the imine Ph2C=NH leads to the partial hydrogenation of the alkylidyne moiety that is supported on the organometallic oxide, [Ti3CP3*O-3], and the formation of new oxoderivatives [{TiCP*(mu-O)}(3)(mu-CHR)(R'NR")] (R" = 2,6-Me2C6H3, R'=H, R=H (3), Me (4); R' = R" = Et, R=H (5), Me (6); R' = R" =Ph, R=H (7), Me (8)) and [{TiCp*(mu-O)}(3)(mu-CHR)(N=CPh2)] (R=H (9), R = Me (10)), respectively. A sequential transfer hydrogenation process occurs when complex 1 is treated with tBuNH(2), which initially gives the p-methylene [{TiCp*(mu-O)}(3)(mu-CH2)(HNtBu)] (11) complex and finally, the alkyl derivative [{TiCp*(mu-O)}(3)(mu-NtBu)Me] (12). Furthermore, irradiation of solutions of the mu(3)-alkylidyne complexes I or 2 in the presence of diamines o-C6H4(NH2)(2) and H2NCH2CH2NH2 (en) affords [{TiCp*(mu-O)}(3)(mu(3)-eta(2)-NC6H4NH)] (13) and [{TiCp*(mu-O)}(3)(mu(3)-eta(2)-NC2H4NH)] (14) by either methane or ethane elimination, respectively. In the reaction of I with en, an intermediate complex [{TiCp*(mu-O)}(3)(mu-CH2)(NH-CH2CH2NH2)] (15) is detected by H-1 NMR spectroscopy. Thermal treatment of the complexes 4-10 quantitatively regenerates the starting mu(3)-alkylidyne compounds and the amine R-2'NH or the imine Ph2C-NH; however, heating of solutions of 3 or 4 in [D-6]benzene or a equimolecular mixture of both at 170degreesC produces methane, ethane, or both, and the complex [{TiCp*(mu-O)}(3){mu(3)-eta(2)-NC6H3(Me)CH2}] (16). The molecular structure of 8 has been established by single-crystal X-ray analysis. |
|---|