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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| Main Authors: | , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
September 13, 2025
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| In: |
Journal of the American Chemical Society
Year: 2025, Volume: 147, Issue: 38, Pages: 35164-35171 |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.5c13214 |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1021/jacs.5c13214
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| Author Notes: | Malte Sellin, James D. Watson, Julia Fischer, Manuel Schmitt, Graham E. Ball, Leslie D. Field, and Ingo Krossing |
| Summary: | 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. |
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| Item Description: | Im Text ist "1" und "+" hochgestellt, "5" und "2" tiefgestellt Gesehen am 20.01.2026 |
| Physical Description: | Online Resource |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.5c13214 |