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

Jach, F., Block, T., Prots, Y., Schmidt, M., Bobnar, M., Pöttgen, R., et al. (2022). Non-innocent cyanido ligands: tetracyanidoferrate(-II) as carbonyl copycat. Dalton Transactions, 1-6. doi:10.1039/d2dt00833e.

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 Creators:
Jach, Franziska1, Author              
Block, Theresa2, Author
Prots, Yurii3, Author              
Schmidt, Marcus4, Author              
Bobnar, Matej1, Author              
Pöttgen, Rainer2, Author
Ruck, Michael5, Author              
Hoehn, Peter6, Author              
Affiliations:
1Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863405              
2External Organizations, ou_persistent22              
3Yuri Prots, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863424              
4Marcus Schmidt, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863415              
5Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863444              
6Peter Höhn, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863419              

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 Abstract: 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.

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Language(s): eng - English
 Dates: 2022-04-062022-04-06
 Publication Status: Published in print
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 Rev. Type: -
 Identifiers: ISI: 000782947600001
DOI: 10.1039/d2dt00833e
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Title: Dalton Transactions
  Abbreviation : Dalton Trans.
Source Genre: Journal
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Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: - Sequence Number: - Start / End Page: 1 - 6 Identifier: ISSN: 1477-9226
CoNE: https://pure.mpg.de/cone/journals/resource/954925269323