Thiocyanate

Thiocyanate
Names
	IUPAC name thiocyanate
Identifiers
3D model (JSmol)	Interactive image;
PubChem CID	9322;
	SMILES C(#N)[S-];
Properties
Chemical formula	CNS-
Molar mass	58.0824
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Thiocyanate (also known as sulphocyanate or thiocyanide or rhodanide) is the anion [SCN]⁻ and the conjugate base of thiocyanic acid. Common compounds include the colourless salts potassium thiocyanate and sodium thiocyanate. Organic compounds containing the functional group SCN are also called thiocyanates. Mercury(II) thiocyanate was formerly used in pyrotechnics.

Thiocyanate is analogous to the cyanate ion, [OCN]⁻, where in oxygen is replaced by sulfur. [SCN]⁻ is one of the pseudohalides, due to the similarity of its reactions to that of halide ions. Thiocyanate was formerly 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:

8 CN⁻ + S₈ → 8 SCN⁻

CN⁻ + S₂O₃²⁻ → SCN⁻ + SO₃²⁻

The latter reaction is catalyzed by the enzyme sulfotransferase known as rhodanase and may be relevant to detoxification of cyanide in the body.

Structure, bonding and coordination chemistry

Resonance structures of the thiocyanate ion

Thiocyanate shares its negative charge approximately equally between sulfur and nitrogen. Consequently, 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^[1].

Organic thiocyanates

Organic and transition metal derivatives of the thiocyanate ion can exist as "linkage isomers." In thiocyanates, the organic group or metal is attached to sulfur: R−S−C≡N has a S-C single bond and a C-N triple bond ^[2]. In isothiocyanates, the substituent is attached to nitrogen: R−N=C=S has a S-C double bond and a C-N double bond

Phenylthiocyanate and phenylisothiocyanate are linkage isomers and are bonded differently

Organic thiocyanates are hydrolyzed to thiocarbamates in the Riemschneider thiocarbamate synthesis.

Test for iron(III)

If [SCN]⁻ is added to a solution containing iron(III) ions (Fe³⁺), a blood red solution is formed due to the formation of [Fe(NCS)(H₂O)₅]²⁺.

The blood-red coloured complex pentaaqua(thiocyanato-N)iron(III), [Fe(NCS)(H₂O)₅]²⁺, indicates the presence of Fe³⁺ in solution

References

^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. p. 326
^ Guy, R. G. "Syntheses and Preparative Applications of Thiocyanates" in "Chemistry of Cyanates and Their Derivatives," vol II. Patai, S., (Editor), John Wiley, 1977. New York

[G&E-1] Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. p. 326

[2] Guy, R. G. "Syntheses and Preparative Applications of Thiocyanates" in "Chemistry of Cyanates and Their Derivatives," vol II. Patai, S., (Editor), John Wiley, 1977. New York

[1]

[2]

v t e Inorganic compounds of carbon and related ions
Compounds	CF CO CO₂ CO₃ CO₄ CO₅ CO₆ COS CS C₂S₂ CS₂ CSe₂ C₃O₂ C₃S₂ SiC
Carbon ions	Carbides [:C≡C:]²⁻, [::C::]⁴⁻, [:C=C=C:]⁴⁻ Cyanide [:C≡N:]⁻ Cyanate [:O−C≡N:]⁻ Thiocyanate [:S−C≡N:]⁻ Fulminate [:C≡N−O:]⁻ Thiofulminate [:C≡N−S:]⁻
Nanostructures	Graphite intercalation compounds Fullerides
Oxides and related	Oxides Nitrides Metal carbonyls Carbonic acid Bicarbonates Carbonates