Cleavage of Dinitrogen from Forming Gas by a Titanium Molecular System under Ambient Conditions

Simple exposure of a hexane solution of [TiCp*Me 3 ] (Cp*=η 5 ‐C 5 Me 5 ) to an atmosphere of commercially available and inexpensive forming gas (H 2 /N 2 mixture, 13.5–16.5 % of H 2 ) at room temperature leads to the methylidene–methylidyne–nitrido cube‐type complex [(TiCp*) 4 (μ 3 ‐CH)(μ 3 ‐CH 2 )(μ 3 ‐N) 2 ] via dinitrogen cleavage. This paramagnetic compound reacts with [D 1 ]chloroform to give the titanium(IV) methylidyne–nitrido species [(TiCp*) 4 (μ 3 ‐CH) 2 (μ 3 ‐N) 2 ], whereas its one‐electron oxidation with AgOTf or [Fe(η 5 ‐C 5 H 5 ) 2 ](OTf) (OTf=O 3 SCF 3 ) yields the diamagnetic ionic derivative [(TiCp*) 4 (μ 3 ‐CH)(μ 3 ‐CH 2 )(μ 3 ‐N) 2 ](OTf). The μ 3 ‐nitrido ligands of the methylidyne–nitrido cubane complex can be protonated with [LutH](OTf) (Lut=2,6‐lutidine) or hydrogenated with NH 3 ⋅ BH 3 to afford μ 3 ‐NH imido moieties.