Molecular Electrochemical Reductive Splitting of Dinitrogen with a Molybdenum Complex** - Université de Montpellier
Article Dans Une Revue Angewandte Chemie International Edition Année : 2022

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

Résumé

Abstract Nitrogen reduction under mild conditions (room T and atmospheric P ), using a non‐fossil source of hydrogen remains a challenge. Molecular metal complexes, notably Mo based, have recently been shown to be active for such nitrogen fixation. We report electrochemical N 2 splitting with a Mo III triphosphino complex [(PPP)MoI 3 ], at room temperature and a moderately negative potential. A Mo IV nitride species was generated, which is confirmed by electrochemistry and NMR studies. The reaction goes through two successive one electron reductions of the starting Mo species, coordination of a N 2 molecule, and further splitting to a Mo IV nitride complex. Preliminary DFT studies support the formation of a bridging Mo I N 2 Mo I dinitrogen dimer evolving to the Mo nitride via a low energy transition state. This example joins a short list of molecular complexes for N 2 electrochemical reductive cleavage. It opens a door to electrochemical proton‐coupled electron transfer (PCET) conversion studies of N 2 to NH 3 .

Domaines

Chimie

Dates et versions

hal-04686694 , version 1 (04-09-2024)

Identifiants

Citer

Lydia Merakeb, Soukaina Bennaamane, Jérémy de Freitas, Eric Clot, Nicolas Mézailles, et al.. Molecular Electrochemical Reductive Splitting of Dinitrogen with a Molybdenum Complex**. Angewandte Chemie International Edition, 2022, 61 (40), pp.e202209899. ⟨10.1002/anie.202209899⟩. ⟨hal-04686694⟩
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