Cleavage of Dinitrogen from Forming Gas by a Titanium Molecular System under Ambient Conditions
Simple exposure of a hexane solution of [TiCp*Me3](Cp* = h5-C5Me5) to an atmosphere of commercially available and inexpensive forming gas (H2/N2 mixture, 13.5-16.5 % of H2) at room temperature leads to the methylidene-methylidyne-nitrido cube-type complex [(TiCp*)4(m3-CH)(m3-CH2)(m3-N)2] via dinitro...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2017 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/38430 |
| Acceso en línea: | http://hdl.handle.net/10017/38430 https://dx.doi.org/10.1002/chem.201700152 |
| Access Level: | acceso abierto |
| Palabra clave: | Cage compounds Methylidyne ligands Nitrides Nitrogen fixation Titanium Química Chemistry |
| Sumario: | Simple exposure of a hexane solution of [TiCp*Me3](Cp* = h5-C5Me5) to an atmosphere of commercially available and inexpensive forming gas (H2/N2 mixture, 13.5-16.5 % of H2) at room temperature leads to the methylidene-methylidyne-nitrido cube-type complex [(TiCp*)4(m3-CH)(m3-CH2)(m3-N)2] via dinitrogen cleavage. This paramagnetic compound reacts with [D1]chloroform to give the titanium(IV) methylidyne-nitrido species [(TiCp*)4(m3-CH)2(m3-N)2], whereas its one-electron oxidation with AgOTf or [Fe(h5-C5H5)2](OTf) (OTf = O3SCF3) yields the diamagnetic ionic derivative [(TiCp*)4(m3-CH)(m3-CH2)(m3-N)2](OTf). The m3-nitrido ligands of the methylidyne-nitridocubane complex can be protonated with [LutH](OTf)(Lut = 2,6-lutidine) or hydrogenated with NH3·BH3 to afford m3-NH imido moieties. |
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