A Dinitrogen Complex without Donor Ligands: Isolation and Characterization of a [Mn(CO)5(η1-N2)]+ Salt
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide 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 N 2 ligands carrying a clear negative partial charge. Here, we present the synthesis, isolation, and characterization of the complex salt [Mn(CO) 5 (η 1 -N 2 )] + [F(Al(OR F ) 3 ) 2 ] − (R F = C(CF 3 ) 3 ) that resulted from the oxidation of Mn 2 (CO) 10 under a dinitrogen atmosphere in pentafluorobenzene solvent. The IR/Raman spectra reveal a high N 2 frequency of 2301/2303 cm –1 close to free N 2 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.
DOI: 10.1021/jacs.5c13214
Authors: Malte Sellin, James D. Watson, Julia Fischer, Manuel Schmitt, Graham E. Ball, Leslie D. Field, Ingo Krossing
Institutions: University of Freiburg, UNSW Sydney, Heidelberg University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funders: National Computational Infrastructure, Australian Government, Deutsche Forschungsgemeinschaft, Universität Heidelberg, University of New South Wales, Albert-Ludwigs-Universität Freiburg, Université de Fribourg, Australian Research Council, National Cancer Institute, Division of Materials Research, HORIZON EUROPE European Research Council
Awards: G1110023947, G1366155583, G1578741624, G328597760, Von neuen ÜbergangsmetallCarbonyl und NitrosylKationen der 5. bis 10. Gruppe zu 'nackten' M+ Synthonen und deren Einsatz für Substitutionsreaktionen, die Aktivierung kleiner Moleküle und die Darstellung von potentiellen Katalysatoren, Innocent Deelectronation Chemistry - From the unified redox scale valid in all solvents to innocent deelectronation chemistry in innocent solvents, G387268724, G402306430, Alkane transformations through binding to metals, OxWCA Von unschuldigen und Ligandbildenden OxidansSalzen zu Synthese und Anwendung reaktiver Erdalkali oder früher ÜbergangsMetallArenKationen [Mx(aren)y]n+
OpenAlex ID: W4414162802