Molecular Electrochemical Reductive Splitting of Dinitrogen with a Molybdenum Complex**

Nitrogen reduction in mild conditions (room T and atmospheric P), using a non-fossil source of hydrogen remains challenge. Molecular metal complexes, notably Mo based, have recently shown to be active for such nitrogen fixation. In this work, we report about the electrochemical N2 splitting with MoIII triphosphino complex [(PPP)MoI3], at room temperature moderately negative potential. A MoIV nitride species was generated, which confirmed by electrochemistry NMR studies. The reaction goes through two successive one electron starting species, coordination an molecule, further complex. Preliminary DFT investigation supports formation bridging MoIN2MoI dinitrogen dimer evolving via low energy transition state. This example joins short list molecular complexes reductive cleavage. It opens door PCET conversion studies NH3