Simple exposure of a hexane solution of [TiCpMe ] (Cp=η -C Me ) to an atmosphere of commercially available and inexpensive forming gas (H /N mixture, 13.5-16.5 % of H ) at room temperature leads to the methylidene-methylidyne-nitrido cube-type complex [(TiCp*) (μ -CH)(μ -CH )(μ -N) ] via dinitrogen cleavage. This paramagnetic compound reacts with [D ]chloroform to give the titanium(IV) methylidyne-nitrido species [(TiCp*) (μ -CH) (μ -N) ], whereas its one-electron oxidation with AgOTf or Fe(η -C H ) (OTf=O SCF ) yields the diamagnetic ionic derivative (TiCp*) (μ -CH)(μ -CH )(μ -N) . The μ -nitrido ligands of the methylidyne-nitrido cubane complex can be protonated with LutH (Lut=2,6-lutidine) or hydrogenated with NH ⋅BH to afford μ -NH imido moieties.