Abstract
The activation and valorization of inert molecules (e.g., dinitrogen (N2), alkanes, and alkenes) for the synthesis of nitrogen-containing organic compounds have long been a highly sought-after goal in chemistry. However, it remains a formidable challenge, stemming from the inherent chemical inertness of the robust N ≡ N and C-H bonds, as well as the competitive adsorption and activation of reactants. Consequently, examples of direct C-N bond formation using N2 and alkanes/alkenes as feedstocks remain exceptionally scarce. Herein, we report that sodium hydride supported on magnesium oxide (NaH/MgO) possesses unique multiple reactive sites, which enable the conversion of N2 and unactivated arenes and facilitate C-N bond formation. The synergistic interplay between sodium, magnesium, and hydride species at the NaH/MgO interface plays a pivotal role in the reduction of N2 to NHx species. These reactive NHx intermediates then deprotonate the aryl C-H bond, attack the alkali-interacted aryl ring, and drive the formation of sodium anilide on the surface. Subsequent protonation of sodium anilide yields aniline with high selectivity (>90%). This work demonstrates the feasibility of transforming N2 and simple arenes into key nitrogen-containing organic compounds via a solid surface-mediated process, thereby opening ample room for developing heterogeneous catalysts for the transformation of N2 and organic substrates.
Data availability
The data generated in this study are provided in the Supplementary Information/Source Data file. Source data are provided with this paper. All data are available from the corresponding author upon request. The data that support the findings of this study are openly available in Figshare at: https://doi.org/10.6084/m9.figshare.31832029. Source data are provided with this paper.
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Acknowledgements
We thank Prof. Kuizhi Chen from Dalian Institute of Chemical Physics for their experimental assistance and fruitful discussions. The authors are grateful for financial support from National Natural Science Foundation of China (Grant No. 22588201) (P.C.) and Youth Innovation Promotion Association CAS (No. Y2022060) (J.G.).
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J.G. and P.C. conceived the project. Y.C. initiated the preliminary experiments. J.G., S.Z. and Y.C. designed the experiments, analyzed the data, and wrote the manuscript. S.Z. and Y.C. conducted the experimental work. H.W. conducted the DFT calculations. L.L., L.Y., and P.Z. reviewed and edited the paper. All authors participated in the discussion and data analyses.
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J.G., S.Z., Y.C., and P.C. are inventors on a patent application that has been submitted by Chinese Academy of Sciences/Dalian Institute of Chemical Physics that covers the synthesis strategy of aniline used in this paper (Patent application number 202511724605.X). The other authors declare no competing interests.
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Zhang, S., Cai, Y., Wen, H. et al. Synthesis of aniline from dinitrogen and benzene mediated by magnesium oxide supported sodium hydride. Nat Commun (2026). https://doi.org/10.1038/s41467-026-71592-9
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DOI: https://doi.org/10.1038/s41467-026-71592-9
