Thiocyanate ions

The thiocyanate ion SCN forms an intensely red-coloured complex (most simply represented as [Fe(SCN)(H20)5] ) which is a test for iron(III). However, unlike cobalt(III), iron(lll) does not form stable hexammines in aqueous solution, although salts containing the ion [FefNHj) ] can be obtained by dissolving anhydrous iron(III) salts in liquid ammonia. 

Copperil) cyanide. CuCN (and copperil) thiocyanate), are similarly obtained as white precipitates on adding cyanide and thiocyanate ions (not in excess) respectively to copper(II) salts ... 

Silver nitrate is used volumetrically to estimate chloride, bromide, cyanide and thiocyanate ions. Potassium chromate or fluorescein is used as an indicator. 

Another hydrometaHurgical use of Caro s acid is for destroying cyanide effluents from gold-leaching. It is more useful than catalyzed hydrogen peroxide for this duty because it also destroys thiocyanate ion. This appHcation has been demonstrated ia the laboratory (66) and at two gold mines (66,67). 

Solvent for Displacement Reactions. As the most polar of the common aprotic solvents, DMSO is a favored solvent for displacement reactions because of its high dielectric constant and because anions are less solvated in it (87). Rates for these reactions are sometimes a thousand times faster in DMSO than in alcohols. Suitable nucleophiles include acetyUde ion, alkoxide ion, hydroxide ion, azide ion, carbanions, carboxylate ions, cyanide ion, hahde ions, mercaptide ions, phenoxide ions, nitrite ions, and thiocyanate ions (31). Rates of displacement by amides or amines are also greater in DMSO than in alcohol or aqueous solutions. Dimethyl sulfoxide is used as the reaction solvent in the manufacture of high performance, polyaryl ether polymers by reaction of bis(4,4 -chlorophenyl) sulfone with the disodium salts of dihydroxyphenols, eg, bisphenol A or 4,4 -sulfonylbisphenol (88). These and related reactions are made more economical by efficient recycling of DMSO (89). Nucleophilic displacement of activated aromatic nitro groups with aryloxy anion in DMSO is a versatile and useful reaction for the synthesis of aromatic ethers and polyethers (90). 

Thiocyanate ion, SCN , inhibits formation of thyroid hormones by inhibiting the iodination of tyrosine residues in thyroglobufin by thyroid peroxidase. This ion is also responsible for the goitrogenic effect of cassava (manioc, tapioca). Cyanide, CN , is liberated by hydrolysis from the cyanogenic glucoside finamarin it contains, which in turn is biodetoxified to SCN. 

Chloride. Chloride is common in freshwater because almost all chloride salts are very soluble in water. Its concentration is generally lO " to 10 M. Chloride can be titrated with mercuric nitrate. Diphenylcarbazone, which forms a purple complex with the excess mercuric ions at pH 2.3—2.8, is used as the indicator. The pH should be controlled to 0.1 pH unit. Bromide and iodide are the principal interferences, whereas chromate, ferric, and sulfite ions interfere at levels greater than 10 mg/L. Chloride can also be deterrnined by a colorimetric method based on the displacement of thiocyanate ion from mercuric thiocyanate by chloride ion. The Hberated SCN reacts with ferric ion to form the colored complex of ferric thiocyanate. The method is suitable for chloride concentrations from 10 to 10 M. 

Iodide and thiocyanate ion are effective catalysts for inducing a related rearrangement (62AG(E)S28). This reaction can be envisioned as proceeding by nucleophilic attack on the lesser substituted aziridinyl carbon atom by iodide ion to give an iodoethyl intermediate such as (132) which is subsequently converted to the final product. 

The reactions of oxiranes with thiocyanate ion or with thiourea are usually done in homogeneous solution in water, alcohols or alcohol-acetic acid. The use of silica gel as a support for potassium thiocyanate in toluene solvent is advantageous for the simple work-up (filtration and evaporation of solvent) (80JOC4254). A crown ether has been used to catalyze reactions of potassium thiocyanate. 

Treatment of cyclic carbonates of 1,2-diols with thiocyanate ion at temperatures of 100 °C or higher yields thiiranes (Scheme 145) (66CRV297, 75RCR138). Thiourea cannot replace thiocyanate satisfactorily, and yields decrease as the carbonate becomes more sterically hindered. The reaction mechanism is similar to the reaction of oxiranes with thiocyanate (Scheme 139). As Scheme 145 shows, chiral thiiranes can be derived from chiral 1,2-diols (77T999, 75MI50600). 

The main chemico-analytical properties of the designed ionoselective electrodes have been determined. The work pH range of the electrodes is 1 to 5. The steepness of the electrode function is close to the idealized one calculated for two-charged ions (26-29 mV/pC). The electrode function have been established in the concentration range from 0.1 to 0.00001 mole/1. The principal advantage of such electrodes is the fact that thiocyanate ions are simultaneously both complexing ligands and the ionic power. The sensitivity (the discovery limits), selectivity (coefficient of selectivity) and the influence of the main temporal factors (drift of a potential, time of the response, lifetime of the membranes) were determined for these electrodes. 

In general, thiocyanate salts are used for the epoxide-thiirane conversions. The reaction proceeds by nucleophilic attack on the epoxide by thiocyanate ion followed by cyclization as shown for (121) (125). The formation of a... 

Pseudohalides of Se in which the role of halogen is played by cyanide, thiocyanate or selenocyanate are known and, in the case of Se are much more stable with respect to disproportionation than are the halides themselves. Examples are Se(CN)2, Se2(CN)2, Se(SeCN)2, Se(SCN)2, Se2(SCN)2. The selenocyanate ion SeCN is ambidentate like the thiocyanate ion, etc., p. 325), being capable of ligating to metal centres via either N or Se, as in the osmium(IV) complexes [OsCl5(NCSe)], [OsCl5(SeCN)], and trans-[OsCU(NCSe)(SeCN)]2-.920) Tellurium and polonium pseudohalogen analogues include Te(CN)2 and Po(CN)4 but have been much... 

Consider the reaction you encountered in the laboratory—that between ferric ion (Fe+3) and thiocyanate ion (SCN ) ... 

By means of colorimetric determination in the laboratory you measured the concentration of FeSCN+i, which we shall designate [FeSCN+2], in solutions containing ferric and thiocyanate ions, Fe+3 and SCN. The reaction is... 

SCN- is the thiocyanate ion). Consider the oxidation number of chromium to be +3 and the coordination number to be 6 in both compounds. Estimate... 

Discussion. Molybdenum(VI) in acid solution when treated with tin(II) chloride [best in the presence of a little iron(II) ion] is converted largely into molybdenum(V) this forms a complex with thiocyanate ion, probably largely Mo(SCN)5, which is red in colour. The latter may be extracted with solvents possessing donor oxygen atoms (3-methylbutanol is preferred). The colour depends upon the acid concentration (optimum concentration 1M) and the concentration of the thiocyanate ion (1 per cent, but colour intensity is constant in the range 2-10 per cent) it is little influenced by excess of tin(II) chloride. The molybdenum complex has maximum absorption at 465 nm. 

These reactions take place with sparingly soluble silver salts, and hence provide a method for the determination of the halide ions Cl", Br, I-, and the thiocyanate ion SCN ". The anion is first precipitated as the silver salt, the latter dissolved in a solution of [Ni(CN)4]2", and the equivalent amount of nickel thereby set free is determined by rapid titration with EDTA using an appropriate indicator (murexide, bromopyrogallol red). 

Mercury(II) thiocyanate method Discussion. This second procedure for the determination of trace amounts of chloride ion depends upon the displacement of thiocyanate ion from mercury(II) thiocyanate by chloride ion in the presence of iron(III) ion a highly coloured iron(III) thiocyanate complex is formed, and the intensity of its colour is proportional to the original chloride ion concentration ... 

Bromo-6,7,8,9-tetrahydro-l//-3-benzazepin-2-amine(6) with thiocyanate ion undergoes substitution of bromide to give the thiocyanatotetrahydro-l//-3-benzazepine 7.105 Attempts to replace bromide by azide ion failed, as did diazotization of the amine group with sodium nitrite in 6 M sulfuric acid. Oddly, treatment of the aminobromo compound with sodium borohydride in methanol results not in reduction, but in methoxy-debromination to give the 2-methoxy derivative which, on the basis of HNMR spectral data, is best represented as the 2-imino tautomer 8. 

Aminodebromination of 4-bromo-l//-3-benzazepin-2-amine (25) with triethylamine occurs readily and results in formation of the quaternary salt 26 (see also Section 3.2.1.5.6.), whereas attempts to effect nucleophilic substitution of bromide with primary or secondary amines gives only tarry mixtures.41 The bromo group is also resistant to displacement by azide and benz-cncthiolate but undergoes substitution with thiocyanate ion in hot dimethylformamide to give the 4-thiocyanato derivative 27 rather than the thiourea by addition at the amine function. 

Nucleophilic catalysis is also observed with iodide ions. Fluoride ion does not form nitrosyl fluoride under diazotization conditions, as is to be expected from Pearson s hard and soft acids and bases principle which was discussed briefly in Section 3.2. More recently, nucleophilic catalysis has also been shown to occur with thiocyanate ion (SCN ), thiosulfate ion (HS2Of), dimethyl sulfide, and thiourea (H2NCSNH2) or its alkyl derivatives (see below). 

One test for the presence of iron(III) ions in solution is to add a solution of potassium thiocyanate, KSCN, and obtain the blood-red color of a compound of iron and the thiocyanate ion. Write three Lewis structures with different atomic arrangements for the... 

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