Titanium-promoted conversion of N2 into N-methylimides

The direct transformation of dinitrogen (N₂) into nitrogen-containing organic compounds holds substantial importance. In this work, we report a titanium-promoted method for the conversion of N 2 to N -methylimides. Initially, the N₂-bridging end-on dititanium side-on dipotassium complex [{(Tren TMS )Ti} 2 (μ-η 1 :η 1 :η 2 :η 2 -N 2 K 2 )] underwent simultaneous disproportionation and N -methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(N Me,TMS NN TMS 2 )Ti}(μ-NMe)] 2 with complete cleavage of the N N bond. The nucleophilicity of the N -methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane (TMSCl) to form heptamethyldisilazane, or with acyl chlorides to generate N -methylimides. Moreover, nitrogen-15 ( 15 N) labeled experiments provided a novel approach to synthesizing 15 N-labeled methylimides. Under ambient conditions, dinitrogen was transformed into N -methylimides through sequential reactions with methyl trifluoromethanesulfonate and acyl chlorides via a four-membered-ring titanium-amido complex.