Ferrocyanide is the name of the anion [Fe(CN)6]4−. Salts of this coordination complex give yellow solutions. It is usually available as the salt potassium ferrocyanide, which has the formula K4Fe(CN)6. [Fe(CN)6]4− is a diamagnetic species, featuring low-spin iron(II) center in an octahedral ligand environment. Although many salts of cyanide are highly toxic, ferro- and ferricyanides are less toxic because they tend not to release free cyanide. It is of commercial interest as a precursor to the pigment Prussian blue and, as its potassium salt, an anticaking agent.
Treatment of ferrocyanide with ferric-containing salts gives the intensely coloured pigment Prussian blue (sometimes called ferric ferrocyanide and ferrous ferricyanide).
Ferrocyanide reversibly oxidized by one electron, giving ferricyanide:
[Fe(CN)6]4− ⇌ [Fe(CN)6]3− + e−
This conversion can be followed spectroscopically at 420 nm, since ferrocyanide has negligible absorption at this wavelength while ferricyanide has an extinction coefficient of 1040 M−1 cm−1.
The dominant use of ferrocyanides is as precursors to the Prussian blue pigments. Sodium ferrocyanide is a common anti-caking agent. Specialized applications involves their use as precipitating agents for production of citric acid and wine.
Ferrocyanide and its oxidized product ferricyanide cannot freely pass through the plasma membrane. For this reason ferrocyanide has been used as a probe of extracellular electron acceptor in the study of redox reactions in cells. Ferricyanide is consumed in the process, thus any increase in ferrocyanide can be attributed to secretions of reductants or transplasma membrane electron transport activity.
Nickel ferrocyanide (Ni2Fe(CN)6) is also used as catalyst in electro-oxidation (anodic oxidation) of urea. Aspirational applications range from hydrogen production for cleaner energy with lower CO2 emission to wastewater treatment.
Ferrocyanide is also studied as an electrolyte in flow batteries.
According to the recommendations of IUPAC, ferrocyanide should be called "hexacyanidoferrate(II)".
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Sodium ferrocyanide is the sodium salt of the coordination compound of formula [Fe(CN)6]4−. In its hydrous form, Na4Fe(CN)6 (sodium ferrocyanide decahydrate), it is sometimes known as yellow prussiate of soda. It is a yellow crystalline solid that is soluble in water and insoluble in alcohol. The yellow color is the color of ferrocyanide anion. Despite the presence of the cyanide ligands, sodium ferrocyanide has low toxicity (acceptable daily intake 0–0.025 mg/kg body weight).
Ferricyanide is the anion [Fe(CN)6]3−. It is also called hexacyanoferrate(III) and in rare, but systematic nomenclature, hexacyanidoferrate(III). The most common salt of this anion is potassium ferricyanide, a red crystalline material that is used as an oxidant in organic chemistry. [Fe(CN)6]3− consists of a Fe3+ center bound in octahedral geometry to six cyanide ligands. The complex has Oh symmetry. The iron is low spin and easily reduced to the related ferrocyanide ion [Fe(CN)6]4−, which is a ferrous (Fe2+) derivative.
Potassium ferrocyanide is the inorganic compound with formula K4[Fe(CN)6]·3H2O. It is the potassium salt of the coordination complex [Fe(CN)6]4−. This salt forms lemon-yellow monoclinic crystals. In 1752, the French chemist Pierre Joseph Macquer (1718–1784) first reported the preparation of potassium ferrocyanide, which he achieved by reacting Prussian blue (iron(III) ferrocyanide) with potassium hydroxide. Potassium ferrocyanide is produced industrially from hydrogen cyanide, ferrous chloride, and calcium hydroxide, the combination of which affords Ca2[Fe(CN)6]·11H2O.
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