(Electro)chemical N2 Splitting by a Molybdenum Complex with an Anionic PNP Pincer-Type Ligand.
ACS Org Inorg Au
; 4(3): 329-337, 2024 Jun 05.
Article
en En
| MEDLINE
| ID: mdl-38855335
ABSTRACT
Molybdenum(III) complexes bearing pincer-type ligands are well-known catalysts for N2-to-NH3 reduction. We investigated herein the impact of an anionic PNP pincer-type ligand in a Mo(III) complex on the (electro)chemical N2 splitting ([LMoCl3]-, 1 -, LH = 2,6-bis((di-tert-butylphosphaneyl)methyl)-pyridin-4-one). The increased electron-donating properties of the anionic ligand should lead to a stronger degree of N2 activation. The catalyst is indeed active in N2-to-NH3 conversion utilizing the proton-coupled electron transfer reagent SmI2/ethylene glycol. The corresponding Mo(V) nitrido complex 2H exhibits similar catalytic activity as 1H and thus could represent a viable intermediate. The Mo(IV) nitrido complex 3 - is also accessible by electrochemical reduction of 1 - under a N2 atmosphere. IR- and UV/vis-SEC measurements suggest that N2 splitting occurs via formation of an "overreduced" but more stable [(L(N2)2Mo0)2µ-N2]2- dimer. In line with this, the yield in the nitrido complex increases with lower applied potentials.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
ACS Org Inorg Au
Año:
2024
Tipo del documento:
Article
País de afiliación:
Alemania
Pais de publicación:
Estados Unidos