Thiocyanate is analogous to the cyanate ion, [OCN]−, wherein oxygen is replaced by sulfur. [SCN]− is one of the pseudohalides, due to the similarity of its reactions to that of halide ions. Thiocyanate used to be known as rhodanide (from a Greek word for rose) 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.[2]
Biological chemistry of thiocyanate in medicine[edit]
Thiocyanate[4] is known to be an important part in the biosynthesis of hypothiocyanite by a lactoperoxidase.[5][6][7] Thus the complete absence of thiocyanate or reduced thiocyanate[8] in the human body, (e.g., cystic fibrosis) is damaging to the human host defense system.[9][10]
Thiocyanate is a potent competitive inhibitor of the thyroid sodium-iodide symporter.[11] 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.[12]
In the early 20th century, thiocyanate was used in the treatment of hypertension, but it is no longer used because of associated toxicity.[13]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 (like other cyanides) with thiosulfate to form the metabolite thiocyanate.
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. [SCN]− can also bridge two (M−SCN−M) or even three metals (>SCN− or −SCN<). Experimental evidence leads to the general conclusion that class A metals (hard acids) tend to form N-bonded thiocyanate complexes, whereas class B metals (soft acids) tend to form S-bonded thiocyanate complexes. Other factors, e.g. kinetics and solubility, are sometimes involved, and linkage isomerism can occur, for example [Co(NH3)5(NCS)]Cl2 and [Co(NH3)5(SCN)]Cl2.[15] It [SCN] is considered as a weak ligand. ([NCS] is a strong ligand)[16]
The blood-red colored (up) complex [Fe(NCS)(H2O)5]2+ (left), indicates the presence of Fe3+ in solution.
If [SCN]− is added to a solution with iron(III) ions, a blood-red solution forms mainly due to the formation of [Fe(SCN)(H2O)5]2+, i.e. pentaaqua(thiocyanato-N)iron(III). Lesser amounts of other hydrated compounds also form: e.g. Fe(SCN)3 and [Fe(SCN)4]−.[17]
Similarly, Co2+ gives a blue complex with thiocyanate.[18] 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(II) in the presence of Fe(III) is possible by adding KF to the solution, which forms uncoloured, very stable complexes with Fe(III), which no longer react with SCN−.[19]
Phospholipids or some detergents aid the transfer of thiocyanatoiron into chlorinated solvents like chloroform and can be determined in this fashion.[20]
^Wilson, I. R.; Harris, G. M. (January 1, 1961). "The oxidation of thiocyanate ion by hydrogen peroxide II: The acid-catalyzed reaction". Journal of the American Chemical Society. 83 (2): 286–289. doi:10.1021/ja01463a007.
^"Hypothyroidism". umm.edu. University of Maryland Medical Center. Retrieved 3 December 2014.
^Warren F. Gorman; Emanuel Messinger; And Morris Herman (1949). "Toxicity of Thiocyanates Used in Treatment of Hypertension". Ann Intern Med. 30 (5): 1054–1059. doi:10.7326/0003-4819-30-5-1054. PMID18126744.
^Palenik, Gus J.; Clark, George Raymond (1970). "Crystal and molecular structure of isothiocyanatothiocyanato-(1-diphenylphosphino-3-dimethylaminopropane)palladium(II)". Inorganic Chemistry. 9 (12): 2754–2760. doi:10.1021/ic50094a028. ISSN0020-1669.
^Uri, N (1947-01-01). "The stability of the cobaltous thiocyanate complex in ethyl alcohol-water mixtures and the photometric determination of cobalt". Analyst. 72 (860): 478–481. Bibcode:1947Ana....72..478U. doi:10.1039/AN9477200478. PMID18917685.
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.[2]
