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 -C₅ Me₅ ) 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 (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 -C₅ H₅ )₂ ](OTf) (OTf=O₃ SCF₃ ) 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 ⋅BH₃ to afford μ₃ -NH imido moieties.