Dinitrogen Binding at a Trititanium Chloride Complex and Its Conversion to Ammonia under Ambient Conditions

Reaction of [TiCp*Cl3] (Cp*=η5-C5Me5) with one equivalent magnesium in tetrahydrofuran at room temperature affords the paramagnetic trinuclear complex [{TiCp*(μ-Cl)}3(μ3-Cl)], which reacts dinitrogen under ambient conditions to give diamagnetic derivative [{TiCp*(μ-Cl)}3(μ3-η1 : η2 η2-N2)] and titanium(III) dimer [{TiCp*Cl(μ-Cl)}2]. The structure mixed-valence complexes has been studied by experimental theoretical methods latter compound represents first well-defined example μ3-η1 coordination mode molecule. reaction excess HCl results clean NH4Cl formation regeneration starting material [TiCp*Cl3]. Therefore, a cyclic ammonia synthesis can be envisioned alternating N2/HCl atmospheres [TiCp*Cl3]/Mg(excess) mixture tetrahydrofuran.