Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2025

Bio‐Inspired Thiolate‐FeII‐Hydrazine Adduct Towards Iron‐Mediated C‐N Bond Formation

Résumé

The bio‐inspired dinuclear iron(II) complex [FeII(L)]₂ (L2‐ = 2,2’‐(2,2’‐bipyridine‐6,6’‐diyl)bis(1,1’‐diphenylethanethiolate)), featuring alkyl thiolate ligands, was found to react with hydrazine (N₂H₄) to form an unprecedented alkyl thiolate‐supported FeII‐N₂H₄ adduct, [LFeII(N₂H₄)]. This complex was characterized structurally by X‐ray crystallography, spectroscopically (1H NMR, UV‐vis, IR), and electrochemically. Unexpectedly, in CH3CN solution, [LFeII(N₂H₄)] gradually evolved to yield an FeII‐acetohydrazonohydrazide complex, [LFeII(H₂N₂C(CH₃)N₂H₃)], the C‐N bond formation resulting from the reaction between N₂H₄ and CH₃CN mediated by the FeII ion. Its structure, confirmed by X‐ray diffraction on single crystals, reveals a η¹‐coordination of the acetohydrazonohydrazide ligand. The proposed mechanism is based on the electrophilic activation of a CH3CN molecule by FeII, followed by the nucleophilic attack of a free hydrazine. This work expands the reactivity landscape of iron‐hydrazine complexes and provides new insights into potential pathways for N‐N bond functionalization in nitrogen fixation processes.

Fichier principal
Vignette du fichier
paper_Irene-N2H4_rev_submission.pdf (840.21 Ko) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)
Licence

Dates et versions

hal-04862118 , version 1 (02-01-2025)

Licence

Identifiants

Citer

Irene Cassandrini, Christian Philouze, Antoine Simonneau, Matthieu Koepf, Carole Duboc, et al.. Bio‐Inspired Thiolate‐FeII‐Hydrazine Adduct Towards Iron‐Mediated C‐N Bond Formation. European Journal of Inorganic Chemistry, 2025, 28 (3), pp.e202400633. ⟨10.1002/ejic.202400633⟩. ⟨hal-04862118⟩
180 Consultations
165 Téléchargements

Altmetric

Partager

  • More