Diiron propanedithiolate hexacarbonyl

Diiron propanedithiolate hexacarbonyl

Identifiers
CAS Number	70789-83-2
3D model (JSmol)	Interactive image
PubChem CID	139250566
InChI InChI=1S/C3H8S2.6CO.2Fe/c4-2-1-3-5;6*1-2;;/h4-5H,1-3H2;;;;;;;;/p-2 Key: ZHHRDZYBLRXFMT-UHFFFAOYSA-L
SMILES O=[C][Fe]12([C]=O)([C]=O)[S]3CCC[S]1[Fe]23([C]=O)([C]=O)[C]=O
Properties
Chemical formula	C9H6Fe2O6S2
Molar mass	385.83
Appearance	red solid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Diiron propanedithiolate hexacarbonyl is the organoiron complex with the formula Fe₂(S₂C₃H₆)(CO)₆. It is a red diamagnetic solid. ^[1] It adopts a symmetrical structure with six terminal CO ligands. ^[2] The complex is a precursor to hydrogenase mimics. ^[3]

It is prepared by the reaction of 1,3-propanedithiol with triiron dodecacarbonyl:

2 Fe₃(CO)₁₂ + 3 C₃H₆(SH)₂ → 3 Fe₂(S₂C₃H₆)(CO)₆ + 3 H₂ + 6 CO

In general, the CO ligands can be substituted by cyanide, phosphines, isocyanides, N-heterocyclic carbenes, and other donor ligands. Monosubstitution can be achieved through an in situ generation of the acetonitrile complex. ^{[4] [5]}

Upon irradiation of Fe₂(S₂C₃H₆)(CO)₆ with ultraviolet (UV) light, CO-photolysis occurs with the transient formation of the unsaturated species followed by the formation of the solvent adduct. ^[6]

References

1. Winter, A., Zsolnai, L., Huttner, G., "Zweikernige und dreikernige Carbonyleisenkomplexe mit 1,2- und 1,3-Dithiolatobrückenliganden", Z. Naturforsch. 1982, 37b, 1430.
2. Lyon, E. J., Georgakaki, I. P., Reibenspies, J. H., Darensbourg, M. Y., "Carbon Monoxide and Cyanide Ligands in a Classical Organometallic Complex Model for Fe-Only Hydrogenase", Angew. Chem. Int. Ed. 1999, 38, 3178.
3. Hogarth, Graeme (2023). "An Unexpected leading role for [Fe₂(CO)₆(μ-PDT)] in our Understanding of [FeFe]-H₂ases and the Search for Clean Hydrogen Production". Coordination Chemistry Reviews. 490. doi:10.1016/j.ccr.2023.215174.
4. Mack, A.; Rauchfuss, T. B., "(1,3-Propanedithiolato)hexacarbonyl and Cyanide Derivatives", Inorganic Synthesis. 2010, volume 35, 143. doi : 10.1002/9780470651568.ch7
5. Works, C., "Laboratory Experiment or Mini-Project for Inorganic Chemistry or Integrated Laboratory", Journal of Chemical Education. 2007, 84, 836.
6. Mack, A. R. Ridley, A. I. Stewart, K. Adamczyk, H. N. Ghosh, B. Kerkeni, Z. X. Guo, E. T. J. Nibbering, C. J. Pickett, N. T. Hunt "(1,3-Propanedithiolato)hexacarbonyl and Cyanide Derivatives", Inorg. Chem. 2008, 47, 7453-7455 doi : 10.1021/ic800568k