Thiocyanate


Thiocyanate is the anion −. It is the conjugate base of thiocyanic acid. Common derivatives include the colourless salts potassium thiocyanate and sodium thiocyanate. Organic compounds containing the functional group SCN are also called thiocyanates. Mercury thiocyanate was formerly used in pyrotechnics.
Thiocyanate is analogous to the cyanate ion, −, wherein oxygen is replaced by sulfur. − is one of the pseudohalides, due to the similarity of its reactions to that of halide ions. Thiocyanate used to be known as rhodanide because of the red colour of its complexes with iron. Thiocyanate is produced by the reaction of elemental sulfur or thiosulfate with cyanide:
The second reaction is catalyzed by thiosulfate sulfurtransferase, a hepatic mitochondrial enzyme, and by other sulfur transferases, which together are responsible for around 80% of cyanide metabolism in the body.

Organic thiocyanates

Organic and transition metal derivatives of the thiocyanate ion can exist as "linkage isomers". In thiocyanates, the organic group is attached to sulfur: R−S−C≡N has a S–C single bond and a C≡N triple bond. In isothiocyanates, the substituent is attached to nitrogen: R−N=C=S has a S=C double bond and a C=N double bond:
Organic thiocyanates are valuable building blocks in organic chemistry and they allow to access efficiently various sulfur containing functional groups and scaffolds.

Synthesis

Several synthesis routes exist, the most basic being the reaction between alkyl halides and alkali thiocyanate in aqueous media. Organic thiocyanates are hydrolyzed to thiocarbamates in the Riemschneider thiocarbamate synthesis.

Biological chemistry of thiocyanate in medicine

Thiocyanate is known to be an important part in the biosynthesis of hypothiocyanite by a lactoperoxidase. Thus the complete absence of thiocyanate or reduced thiocyanate in the human body, is damaging to the human host defense system.
Thiocyanate is a potent competitive inhibitor of the thyroid sodium-iodide symporter. Iodine is an essential component of thyroxine. Since thiocyanates will decrease iodide transport into the thyroid follicular cell, they will decrease the amount of thyroxine produced by the thyroid gland. As such, foodstuffs containing thiocyanate are best avoided by Iodide deficient hypothyroid patients.
In the early 20th century, thiocyanate was used in the treatment of hypertension, but it is no longer used because of associated toxicity. Sodium nitroprusside, a metabolite of which is thiocyanate, is however still used for the treatment of a hypertensive emergency. Rhodanese catalyzes the reaction of sodium nitroprusside with thiosulfate to form the metabolite thiocyanate.

Coordination chemistry

Thiocyanate shares its negative charge approximately equally between sulfur and nitrogen. As a consequence, thiocyanate can act as a nucleophile at either sulfur or nitrogen — it is an ambidentate ligand. − can also bridge two or even three metals. Experimental evidence leads to the general conclusion that class A metals tend to form N-bonded thiocyanate complexes, whereas class B metals tend to form S-bonded thiocyanate complexes. Other factors, e.g. kinetics and solubility, are sometimes involved, and linkage isomerism can occur, for example Cl2 and Cl2.

Test for iron(III) and cobalt(II)

If − is added to a solution with iron ions, a blood-red solution forms mainly due to the formation ofthiocyanatoiron| 2+, i.e. pentaaquairon. Lesser amounts of other hydrated compounds also form: e.g. Fe3 and −.
Similarly, Co2+ gives a blue complex with thiocyanate. Both the iron and cobalt complexes can be extracted into organic solvents like diethyl ether or amyl alcohol. This allows the determination of these ions even in strongly coloured solutions. The determination of Co in the presence of Fe is possible by adding KF to the solution, which forms uncoloured, very stable complexes with Fe, which no longer react with SCN−.
Phospholipids or some detergents aid the transfer of thiocyanatoiron into chlorinated solvents like chloroform and can be determined in this fashion.

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