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N2 Reduction versus H2 Evolution in a Molybdenum‐ or Tungsten‐Based Small‐Molecule Model System of Nitrogenase

The selectivity between the reduction of dinitrogen (N2RR) and the evolution of hydrogen (HER) is investigated experimentally and by DFT calculations based on Mo- and W-based model systems. Moreover, possible reaction mechanisms for N2RR, as well as for HER, are determined and discussed in detail.


Molybdenum dinitrogen complexes have played a major role as catalytic model systems of nitrogenase. In comparison, analogous tungsten complexes have in most cases found to be catalytically inactive. Herein, a tungsten complex was shown to be supported by a pentadentate tetrapodal (pentaPod) phosphine ligand, under conditions of N2 fixation, primarily catalyzes the hydrogen evolution reaction (HER), in contrast to its Mo analogue, which catalytically mediates the nitrogen-reduction reaction (N2RR). DFT calculations were employed to evaluate possible mechanisms and identify the most likely pathways of N2RR and HER activities exhibited by Mo- and W-pentaPod complexes. Two mechanisms for N2RR by PCET are considered, starting from neutral (M(0) cycle) and cationic (M(I) cycle) dinitrogen complexes (M=Mo, W). The latter was found to be energetically more favorable. For HER three scenarios are treated; that is, through bimolecular reactions of early M-NxHy intermediates, pure hydride intermediates or mixed M(H)(NxHy) species.

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