Cleavage of Dinitrogen from Forming Gas by a Titanium Molecular System under Ambient Conditions.
Simple exposure of a hexane solution of [TiCp*Me3] (Cp*=η5-C5Me5) to an atmosphere of commercially available and inexpensive forming gas (H2/N2mixture, 13.5-16.5 % of H2) at room temperature leads to the methylidene-methylidyne-nitrido cube-type complex [(TiCp*)4(μ3-CH)(μ3-CH2)(μ3-N)2] via dinitrogen cleavage. This paramagnetic compound reacts with [D1]chloroform to give the titanium(IV) methylidyne-nitrido species [(TiCp*)4(μ3-CH)2(μ3-N)2], whereas its one-electron oxidation with AgOTf or [Fe(η5-C5H5)2](OTf) (OTf=O3SCF3) yields the diamagnetic ionic derivative [(TiCp*)4(μ3-CH)(μ3-CH2)(μ3-N)2](OTf). The μ3-nitrido ligands of the methylidyne-nitrido cubane complex can be protonated with [LutH](OTf) (Lut=2,6-lutidine) or hydrogenated with NH3⋅BH3to afford μ3-NH imido moieties.
Departamento de Química Orgánica y Química Inorgánica, Universidad de Alcalá, 28805, Alcalá de Henares-Madrid, Spain.
Mariano
M
González-Moreiras
Departamento de Química Orgánica y Química Inorgánica, Universidad de Alcalá, 28805, Alcalá de Henares-Madrid, Spain.
Miguel
http://orcid.org/0000-0001-7456-1212
M
Mena
Departamento de Química Orgánica y Química Inorgánica, Universidad de Alcalá, 28805, Alcalá de Henares-Madrid, Spain.
Adrián
http://orcid.org/0000-0002-0086-8825
A
Pérez-Redondo
Departamento de Química Orgánica y Química Inorgánica, Universidad de Alcalá, 28805, Alcalá de Henares-Madrid, Spain.
Carlos
http://orcid.org/0000-0003-0425-4799
C
Yélamos
cage compounds; methylidyne ligands; nitrides; nitrogen fixation; titanium