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N2 is fixed as NH3 industrially by the Haber–Bosch process under harsh conditions, whereas biological nitrogen fixation is achieved under ambient conditions, which has prompted development of alternative methods to fix N2 catalyzed by transition metal molecular complexes. Since the early 21st century, catalytic conversion of N2 into NH3 under ambient conditions has been achieved by using molecular catalysts, and now H2O has been utilized as a proton source with turnover frequencies reaching the values found for biological nitrogen fixation. In this review, recent advances in the development of molecular catalysts for synthetic N2 fixation under ambient or mild conditions are summarized, and potential directions for future research are also discussed.

Graphical abstract: Comprehensive insights into synthetic nitrogen fixation assisted by molecular catalysts under ambient or mild conditions

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