Silver i

Siher(Il) oxide, AgO, is a black solid, Ag Ag 02, obtained by anodic or persulphate oxidation of an AgNOs solution. Continued anodic oxidation gives impure Ag203. Argentates, e.g. K.AgO, containing silver(I) are known. 

Alonso C, Salvarezza R C, Vara J M and Arvia A J 1990 The meohanism of silver (I) oxide formation on polyorystalline silver in alkaline solution. Determination of nuoleation and growth rates Electrochim. Acta 35 489-96... 

Although the data for the silver halides suggest that silver(I) fluoride is likely to be more soluble than the other silver halides (which is in fact the case), the hydration enthalpies for the sodium halides almost exactly balance the lattice energies. What then is the driving force which makes these salts soluble, and which indeed must be responsible for the solution process where this is endothermic We have seen on p. 66 the relationship AG = — TAS and... 

These are practically insoluble in water, are not hydrolysed and so may be prepared by addition of a sufficient concentration of sulphide ion to exceed the solubility product of the particular sulphide. Some sulphides, for example those of lead(II), copper(II) and silver(I), have low solubility products and are precipitated by the small concentration of sulphide ions produced by passing hydrogen sulphide through an acid solution of the metal salts others for example those of zincfll), iron(II), nickel(II) and cobalt(II) are only precipitated when sulphide ions are available in reasonable concentrations, as they are when hydrogen sulphide is passed into an alkaline solution. 

Bromine is used in the manufacture of many important organic compounds including 1,2-dibromoethane (ethylene dibromide), added to petrol to prevent lead deposition which occurs by decomposition of the anti-knock —lead tetraethyl bromomethane (methyl bromide), a fumigating agent, and several compounds used to reduce flammability of polyester plastics and epoxide resins. Silver(I) bromide is used extensively in the photographic industry... 

The complexes of copper(I) like those of silver(I) (p. 430), but unlike those of preceding transitions metals, tend to prefer a linear coordination of two ligands, i.e. X—Cu—X thus copper(I) chloride in aqueous ammonia gives the colourless [Cu(NH3)2] (readily oxidised in air to give blue [Cu (NH3)4(H20)2] copper(I) chloride in hydrochloric acid gives [CuClj], although [CuCl3] is also known. 

Silver has little tendency to formally lose more than one electron its chemistry is therefore almost entirely restricted to the + 1 oxidation state. Silver itself is resistant to chemical attack, though aqueous cyanide ion slowly attacks it, as does sulphur or a sulphide (to give black Ag S). hence the tarnishing of silver by the atmosphere or other sulphur-containing materials. It dissolves in concentrated nitric acid to give a solution of silver(I) nitrate. AgNOj. 

Addition of an alkali hydroxide to a solution of a silver(I) salt gives a brown solid, silver(I) oxide, AgjO when wet, this behaves as silver hydroxide AgOH, for example... 

The oxide is soluble in ammonia to give the complex [AglNHjlj] (linear). On heating, silver(I) oxide loses oxygen to give the metal (all the coinage metal oxides have low thermal stability and this falls in the order Cu > Ag > Au). 

The chloride is white, the bromide pale yellow and the iodide deeper yellow. These are examples (uncommon) of a coloured compound being obtained from colourless ions. The silver(I) ion intensifies colour in other cases, for example silver chromate(VI), Ag2Cr04, is brick-red while potassium chromaie(VI). K2Cr04. is yellow. 

In neutral solution, the indicator is potassium chromate(VI). In acid solution the CrOj" ion changes to CrjO (p. 378). and since silver dichromatefVI) is soluble, chromate(VI) is not a suitable indicator other methods can be used under these conditions. (In alkaline solution, silverfl) oxide precipitates, so silver(I) nitrate cannot be used under these conditions.)... 

Some of these have already been noted as 2-coordinate and linear, for example [AgfCN) ]". [Ag(NH3)2]+. [AgfS Oj)] ". Silver(I) halides dissolve in concentrated aqueous halide solutions to give complexes [AgX ]", [AgXj]. for example [AgClj] . 

If a bromomethyl- or vinyl-substituted cyclopropane carbon atom bears a hydroxy group, the homoallyiic rearrangement leads preferentially to cyclobutanone derivatives (J. Sa-laun, 1974). Addition of amines to cydopropanone (N. J. Turro, 1966) yields S-lactams after successive treatment with tert-butyl hypochlorite and silver(I) salts (H.H. Wasserman, 1975). For intramolecular cyclopropane formation see section 1.16. 

Stereoselective cis-dihydroxylation of the more hindered side of cycloalkenes is achieved with silver(I) or copper(II) acetates and iodine in wet acetic acid (Woodward gly-colization J.B. Siddall, 1966 L. Mangoni, 1973 R. Criegee, 1979) or with thallium(III) acetate via organothallium intermediates (E. Glotter, 1976). In these reactions the intermediate dioxolenium cation is supposed to be opened hydrolytically, not by Sn2 reaction. 

Hydantoin itself can be detected ia small concentrations ia the presence of other NH-containing compounds by paper chromatography followed by detection with a mercury acetate—diphenylcarba2one spray reagent. A variety of analytical reactions has been developed for 5,5-disubstituted hydantoias, due to their medicinal iaterest. These reactions are best exemplified by reference to the assays used for 5,5-diphenylhydantoiQ (73—78), most of which are based on their cycHc ureide stmcture. Identity tests iaclude the foUowiag (/) the Zwikker reaction, consisting of the formation of a colored complex on treatment with cobalt(II) salts ia the presence of an amine (2) formation of colored copper complexes and (3) precipitation on addition of silver(I) species, due to formation of iasoluble salts at N. ... 

Table 1. Solubility and Solubility Products of Silver(I) Compounds...

Silver(II) Compounds. Sdver(II) is stabilized by coordination with nitrogen heterocychc bases, such as pyridine and dipyridyl. These cationic complexes are prepared by the peroxysulfate oxidation of silver(I) solutions in the presence of an excess of the ligand. An extensive review of the higher oxidation states of silver has beenpubhshed (21). 

Further versatihty was added to the range of substituents available for introduction into the 6a-position by use of the 6a(succinimido-oxy) derivative (18) prepared by treatment of the 6a-(methylthio) derivative (17) with A/-hydroxy-succinimide and silver(I) acetate in dimethylformamide in virtually quantitative yield. In this way the 6a-cyanopeniciILin (19, X = CN), 6a-viny1penici11in (19, X = CH=CH2) and 6a-pheny1penici11in (19, X = C H ) could be prepared in high yield (43). 

Consequent potentiometric titration of osmium(IV) and laithenium (IV) in their mixtures has been canied out in broad range of concentrations from 1 mkg to 200 mkg in samples of 20 ml. It has been shown the possibility of amperemetric determination of osmium(VI) in binary and triple systems with silver(I), platinum(IV), palladium(II), gold(III), founded on formation of corresponding compounds with dimerkaptotiopiron, having a different solubility. The deteriuination of Os(VI) is possible under tenfold - hundredfold excess of above mentioned metals. 

Silver(I) oxide [20667-12-3] M 231.7, m -200 (dec), d 7.13. Leached with hot water in a Soxhlet apparatus for several hours to remove any entrained electrolytes. 

Crude methyl 2-bromostearate (33 g, 0 087 mol) is dissolved in 200 mL of acetonitrile containing 0 5 mL of water, and silver(I) fluonde (50 g, 0 393 mol) is added rapidly in one portion The slurry is stirred vigorously for 20 h in an oil bath at 80 C At the end ot this time thin-layer chromatographic analysis (petroleum... 

The regiochemistry is determined by the regiochemistry of the fluoride ion addition reaction, that is, via the most stable perfluorocarbanion intermediate Von Werner used a similar reaction to prepare silver compounds from perfluoro-2-methyl-2-butene and perfluoro 2 methyl-2-pentene [271] Silver(I) fluoride adds to bis(ttitluoromethyl)ketene in DMF without fluoride ion catalysis [270] The analogous trifluorovinylsulfurpentafluoride reacts similarly to give the isolable pentafluorosulfur derivative [272] (equation 187)... 

Silver(I) triflate is widely applied to the preparation of various derivatives of triflic acid, both covalent esters [66] and ionic salts For example, it can be used for the in situ generation of iodine([) triflate, a very effective lodinatmg reagent for aromatic and heteroaromatic compounds [130] (equations 65 and 66)... 

Silver(I) Inflate and copper(I) triflate can be applied as catalysts A representative example is the preparation of alkynyl tosylates by the catalytic decomposition of alkynyl lodonium salts in the presence of these salts [727] (equation 67)... 

In the reactions of 10.13a with alkali metal terr-butoxides cage expansion occurs to give the sixteen-atom cluster 10.15, in which two molecules of MO Bu (M = Na, K) are inserted into the dimeric structure. The cluster 10.13a also undergoes transmetallation reactions with coinage metals. For example, the reactions with silver(I) or copper(I) halides produces complexes in which three of the ions are replaced by Ag" or Cu" ions and a molecule of lithium halide is incorporated in the cluster. ... 

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