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

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

  • Franziska Jach - , Professur für Anorganische Chemie (II) (AC2) (Autor:in)
  • Theresa Block - , Westfälische Wilhelms-Universität Münster (Autor:in)
  • Yurii Prots - , Max-Planck-Institut für Chemische Physik fester Stoffe (Autor:in)
  • Marcus Schmidt - , Max-Planck-Institut für Chemische Physik fester Stoffe (Autor:in)
  • Matej Bobnar - , Max-Planck-Institut für Chemische Physik fester Stoffe (Autor:in)
  • Rainer Pöttgen - , Westfälische Wilhelms-Universität Münster (Autor:in)
  • Michael Ruck - , Professur für Anorganische Chemie (II) (AC2) (Autor:in)
  • Peter Höhn - , Max-Planck-Institut für Chemische Physik fester Stoffe (Autor:in)

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− 57Fe Mössbauer spectroscopic measurements reveal a negative isomer shift in agreement with substantially delocalized d electrons due to strong π 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 d10 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.

Details

OriginalspracheEnglisch
Seiten (von - bis)7811-7816
Seitenumfang6
FachzeitschriftDalton Transactions
Jahrgang51
Ausgabenummer20
PublikationsstatusVeröffentlicht - 6 Apr. 2022
Peer-Review-StatusJa

Externe IDs

Scopus 85129750404
WOS 000782947600001
ORCID /0000-0002-2391-6025/work/142250226

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Bibliotheksschlagworte