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A dinitrogen complex without donor ligands: isolation and characterization of a (Mn(CO)5(η1-N2))+ salt

Dinitrogen complexes are intermediates in nitrogen fixation. Until now, all isolated molecular dinitrogen complexes have relied on ancillary ligands that are net electron donors, yielding N2 ligands carrying a clear negative partial charge. Here, we present the synthesis, isolation, and characteriza...

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Bibliographische Detailangaben
Hauptverfasser: Sellin, Malte (VerfasserIn) , Watson, James D. (VerfasserIn) , Fischer, Julia (VerfasserIn) , Schmitt, Manuel (VerfasserIn) , Ball, Graham E. (VerfasserIn) , Field, Leslie D. (VerfasserIn) , Krossing, Ingo (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: September 13, 2025
In: Journal of the American Chemical Society
Year: 2025, Jahrgang: 147, Heft: 38, Pages: 35164-35171
ISSN:1520-5126
DOI:10.1021/jacs.5c13214
Online-Zugang:Verlag, kostenfrei, Volltext: https://doi.org/10.1021/jacs.5c13214
Volltext
Verfasserangaben:Malte Sellin, James D. Watson, Julia Fischer, Manuel Schmitt, Graham E. Ball, Leslie D. Field, and Ingo Krossing
Beschreibung
Zusammenfassung:Dinitrogen complexes are intermediates in nitrogen fixation. Until now, all isolated molecular dinitrogen complexes have relied on ancillary ligands that are net electron donors, yielding N2 ligands carrying a clear negative partial charge. Here, we present the synthesis, isolation, and characterization of the complex salt [Mn(CO)5(η1-N2)]+[F(Al(ORF)3)2]− (RF = C(CF3)3) that resulted from the oxidation of Mn2(CO)10 under a dinitrogen atmosphere in pentafluorobenzene solvent. The IR/Raman spectra reveal a high N2 frequency of 2301/2303 cm-1 close to free N2 gas (2330 cm-1) that indicates little π-back-donation. QTAIM and CD-NOCV analyses show that the carbonyl ligands act as net acceptor ligands that induce the formation of an inversely polarized dinitrogen ligand with a +0.2 charge on the terminal atom that holds the potential to be susceptible to nucleophilic attack.
Beschreibung:Im Text ist "1" und "+" hochgestellt, "5" und "2" tiefgestellt
Gesehen am 20.01.2026
Beschreibung:Online Resource
ISSN:1520-5126
DOI:10.1021/jacs.5c13214

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