Non-innocent cyanido ligands: tetracyanidoferrate(-ii) as carbonyl copycat

While a negative oxidation state occurs rarely for metals in general, this is commonly known for metal carbonyl anions, i.e. carbonyl metalates. Although CO and CN- are isoelectronic, cyanidometalates usually do not exhibit metal centers with negative oxidation states. However, we report on the electron-rich tetrahedral tetracyanidoferrate(-ii) anion [Fe(CN)(4)](6-), which was stabilized in (Sr3N)(2)[Fe(CN)(4)] (space group R3c, a = 702.12(2) pm, c = 4155.5(2) pm). Microcrystalline powders were synthesized by a solid-state route, single crystals were obtained from Na metal flux. In comparison to classical cyanidometalates, C-N distances are longer and stretching frequencies are lower as indicated by X-ray diffraction, IR and Raman spectroscopy. Weak C-N, strong Fe-C bonds as well as the anion geometry resemble the isoelectronic tetrahedral carbonyl ferrate [Fe(CO)(4)](2-). Fe-57 Mossbauer spectroscopic measurements reveal a negative isomer shift in agreement with substantially delocalized d electrons due to strong pi back-bonding. These results point to a very similar bonding situation of both 18e tetracyanido and tetracarbonyl ferrates including non-innocent redox-active ligands and a d(10) closed shell configuration on iron. Hereby, new tetracyanidoferrate(-ii) provides a missing link for a more in-depth understanding of the chemical bonding trends of highly-reduced cyanidometalates in the quest for even higher reduced transition metals in this exceptional class of compounds.