ConspectusNitrogen fixation is an essential chemical process both biologically and industrially. Since the discovery of the first transition-metal-dinitrogen complex in 1965, a great deal of effort has been devoted to the development of artificial nitrogen fixation systems that work under mild reaction conditions. However, the transformation of chemically inert dinitrogen using homogeneous catalysts is still challenging because of the difficulty in breaking the strong triple bond of dinitrogen, and a very limited number of transition metal complexes have exhibited the catalytic activity for the direct transformation of dinitrogen into ammonia with low turnover numbers. To develop more effective nitrogen fixation systems, it is necessary to retrieve as much information as possible from the limited successful examples. Computational chemistry will provide valuable insights in the understanding of the reaction mechanisms involving unstable intermediates that are hard to isolate or characterize. We have been applying it for clarifying detailed mechanisms of dinitrogen activation and functionalization by transition metal complexes as well as for designing new catalysts for more effective nitrogen fixation.This Account summarizes recent progress in the elucidation of catalytic mechanisms of nitrogen fixation by using mono- and dinuclear molybdenum complexes, as well as cubane-type metal-sulfido clusters from a theoretical point of view. First, we briefly introduce experimental and theoretical contributions to the elucidation of the reaction mechanism of nitrogen fixation catalyzed by a mononuclear Mo-triamidoamine complex. Special attention is paid to our recent studies on Mo-catalyzed nitrogen fixation using dinitrogen-bridged dimolybdenum complexes. A possible catalytic mechanism is proposed based on theoretical and experimental investigations. The catalytic mechanism involves the formation of a monuclear molybdenum-nitride (Mo-N) intermediate, as well as the regeneration of a dimolybdenum intermediate with the Mo-N-N-Mo moiety. Comparison of the reactivity of di- and monomolybdenum complexes suggests that the dimolybdenum structure is essential for the catalytic activity. Synergy between the two Mo cores connected with a bridging N2 ligand is observed in the protonation of coordinated N2. Intermetallic electron transfer through the bridging N2 ligand reductively activates the coordinated N2 to be protonated. On the basis of the proposed catalytic mechanism, we used DFT calculations for rational design of dimolybdenum complexes serving as more effective catalysts for nitrogen fixation. Newly prepared dimolybdenum complexes with modified PNP-type pincer ligands exhibit greater catalytic activity than the original one.
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