Article Dans Une Revue Angewandte Chemie International Edition Année : 2022

Molecular Electrochemical Reductive Splitting of Dinitrogen with a Molybdenum Complex

Résumé

Nitrogen reduction in mild conditions (i.e., room T and atmospheric P), using a non-fossil source of hydrogen remains a chemistry 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 and a moderately negative potential. A MoIV nitride species was generated, which was confirmed by electrochemistry and NMR studies. The reaction goes through two successive one electron reduction of the starting Mo species, coordination of an N2 molecule, and further splitting to a MoIV nitride complex. Preliminary DFT investigation supports the intermediacy of a bridging MoIN2MoI dinitrogen dimer evolving to the Mo nitride via a low energy transition state. This example joins a short list of molecular electrochemical complexes for N2 reductive cleavage. It opens a door to molecular electrochemical PCET conversion studies of N2 to NH3.
Fichier principal
Vignette du fichier
MS Robert - revised.pdf (1.09 Mo) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03758536 , version 1 (23-08-2022)

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, In press, 7 p. ⟨10.1002/anie.202209899⟩. ⟨hal-03758536⟩
109 Consultations
920 Téléchargements

Altmetric

Partager

More