Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 Aug 8;61(32):e202204080.
doi: 10.1002/anie.202204080. Epub 2022 Jun 7.

Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts

Affiliations

Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts

Jan M Rall et al. Angew Chem Int Ed Engl. .

Abstract

The open-shell iron pentacarbonyl cation [Fe(CO)5 ].+ was isolated by deelectronation, i.e., the single-electron oxidation of the parent neutral Fe(CO)5 using [phenazineF ].+ as the [Al(ORF )4 ]- and [F-{Al(ORF )3 }2 ]- salt (RF =C(CF3 )3 ; phenazineF =perfluoro-5,10-bis(perfluorophenyl)-5,10-dihydrophenazine). [Fe(CO)5 ].+ [Al(ORF )4 ]- was fully characterized (scXRD analysis, IR, NMR, EPR, 57 Fe spectroscopy, CV and SQUID magnetization study) and, apart from being a compound of fundamental interest, may serve as a precursor for low-valent iron coordination chemistry.

Keywords: Carbonyl Ligands; Iron; Radical Ions; Weakly Coordinating Anions.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
a) Molecular structure of [Fe(CO)5].+[Al(ORF)4] (1) (P212121, R 1=5.4 %, wR 2=9.0 %); thermal ellipsoids set at 50 % probability. b) Experimental ZnSe‐ATR FT‐IR spectrum of solid 1. c) Experimental and simulated Q‐band (34 GHz), continuous‐wave EPR spectra of solid 1 at 100 K, a potential impurity is marked by an asterisk. d) The carbonyl region of experimental ZnSe‐ATR FT‐IR spectrum of solid 1 (black), 1 in 4FB (gray), solid 2 (green) and calculated (@BP86‐(D3BJ)/def2‐TZVPP) 13C IR spectrum of the superposition of all possible isotopomers weighed by their natural abundance (blue). Double or more 13C substitution were neglected.
Figure 2
Figure 2
Zero‐field 57Fe Mössbauer spectrum of a solid sample of 1 recorded at 77 K (left). The gray circles are experimental data and the solid black line represents the numerical fit. Cyclic voltammogram of 1 (10 mM) in 4FB with [NBu4][Al(ORF)4] as conducting salt (right). Measurements were done at sweep rates of 20, 50 and 100 mV s−1. The half‐wave potential was found to be independent of the sweep rate.

References

    1. Mond L., Langer C., Quincke F., J. Chem. Soc. 1890, 57, 749–753.
    1. Mond L., Langer C., J. Chem. Soc. Dalton Trans. 1891, 59, 1090–1093.
    1. Ellis J. E., Organometallics 2003, 22, 3322–3338.
    1. Hieber W., Leutert F., Ber. Dtsch. Chem. Ges. 1931, 64, 2832–2839.
    1. Fischer E. F., Fichtel K., Öfele K., Chem. Ber. 1962, 95, 249–252.

LinkOut - more resources