Nitrogen fixation is confronted with great challenges in the field of chemistry. Herein, we report that single metal carbides PtC n − and PtC n N 2 − (n = 4−6) are indispensable intermediates in the process of nitrogen fixation by mass spectrometry coupled with anionic photoelectron spectroscopy, quantum chemical calculations, and simulated density-of-state spectra. The most stable isomers of these cluster anions are characterized to have linear chain structures. The fixation and activation of dinitrogen are facilitated by the charge transfer from Pt and C n to N 2 . The significance of π back-donation of the 5d orbital of the Pt atom to the antibonding π orbits of N 2 for dinitrogen fixation and activation is discussed in detail. This study not only provides a theoretical basis at the molecular level for the activation of dinitrogen by mononuclear metal carbide clusters but also provides a new paradigm for dinitrogen fixation.

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