Citation: Rui Hu, Yidan Qi, Xingyu Wang, Yunhui Yang, Congyang Wang. Titanium-promoted conversion of N₂ into N-methylimides[J]. Chinese Chemical Letters, ;2026, 37(1): 111197. doi: 10.1016/j.cclet.2025.111197 shu

Titanium-promoted conversion of N₂ into N-methylimides

Rui Hu ^{a, b} ,
Yidan Qi ^{a, b} ,
Xingyu Wang ^{a, b} ,
Yunhui Yang ^{a, b, *,} ,
Congyang Wang ^{a, b, *,}

a.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China

yangyh@iccas.ac.cn

wangcy@iccas.ac.cn

Received Date: 15 February 2025
Revised Date: 31 March 2025
Accepted Date: 10 April 2025
Available Online: 11 April 2025

Figures(5)

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 N₂ to N-methylimides. Initially, the N₂-bridging end-on dititanium side-on dipotassium complex [{(Tren^TMS)Ti}₂(μ-η¹:η¹:η²:η²-N₂K₂)] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(N^{Me, TMS}NN₂^TMS)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 (¹⁵N) labeled experiments provided a novel approach to synthesizing ¹⁵N-labeled methylimides.
- Dinitrogen fixation,
- Titanium,
- Imides,
- Heptamethyldisilazane,
- Disproportionation
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Titanium-promoted conversion of N₂ into N-methylimides