Complexes of silver

The precipitated acetyHde must be decomposed with hydrochloric acid after the titration as a safety measure. Concentrated solutions of silver nitrate or silver perchlorate form soluble complexes of silver acetyHde (89). Ammonia and hydrogen sulfide interfere with the silver nitrate method which is less... 

Sulfur Complexes. Silver compounds other than sulfide dissolve in excess thiosulfate. Stable silver complexes are also formed with thiourea. Except for the cyanide complexes, these sulfur complexes of silver are the most stable. In photography, solutions of sodium or ammonium thiosulfate fixers are used to solubilize silver hahdes present in processed photographic emulsions. When insoluble silver thiosulfate is dissolved in excess thiosulfate, various silver complexes form. At low thiosulfate concentrations, the principal silver species is Ag2(S203) 2j high thiosulfate concentrations, species such as Ag2(S203) 3 are present. Silver sulfide dissolves in alkaline sulfide solutions to form complex ions such as Ag(S 2 Ag(HS) 4. These ions are... 

A number of thiourea complexes of silver have shown the tendency to bind up to four ligands, in contrast to gold. Thus Agtu2X (X = Cl, NCS) have essentially 3-coordinate silver (one distant fourth atom) Agtu3C104 is a 4-coordinate dimer (Figure 4.12) [58]. 

Fluoride complexes of silver(III) are exemplified by the purple-red Cs2KAgF6 (elpasolite structure, octahedral Ag3+ paramagnetic with /x = 2.6/ub). Yellow MAgF4 (M = Na, Rb, K) and XeF AgF4 are diamagnetic and probably square planar [65],... 

When ceric ions were substituted for chromic acid, the reaction was still zero-order with respect to metal ion, the rate of reduction of which was unchanged. The mechanism favoured by the authors depends on formation of a complex of silver ions and hydrogen, viz. 

Bruce, D.W. and Hudson, S.A. (1994) Mesomorphic complexes of silver trifluoromethane sulfonate and silver dodecylsulfate with 2- and 3-fluoro-4-alkoxy-4-stilbazoles. Journal of Materials Chemistry, 4, 479-486. 

Marcos, M., Ros, M.B., Serrano, J.L., Sola, M.A., Oro, L.A. and Barbera, J. (1990) Liquid-crystal behavior in ionic complexes of silver(I) molecular structure-mesogenic activity relationship. Chemistry of Materials, 2, 748-758. 

Seward, T.M. (1976) The stability of chloride complexes of silver in hydrothermal ore solutions. Geochim. Cosmochim. Acta, 37, 379-399. 

The development of more benign alternatives to cyanide for gold-leaching (see Section 9.17.3.1) such as thiourea, thiocyanate, or thiosulfate, which form stable complexes in water has prompted research to identify suitable solvent extractants from these media. Cyanex 301, 302, 272, Ionquest 801, LIX 26, MEHPA, DEHPA, Alamine 300 (Table 5) have been evaluated as extractants for gold or silver from acidic thiourea solutions.347 Whilst the efficacy of Cyanex 301 and 302 was unaffected by the presence of thiourea in the aqueous feed, the loading of the other extractants is severely depressed. Formation of solvated complexes of gold and of an inner-sphere complex of silver has been proposed.347... 

The shift in the C=C frequency, vi, for adsorbed ethylene relative to that in the gas phase is 23 cm-1. This is much greater than the 2 cm-1 shift that is observed on liquefaction (42) but is less than that found for complexes of silver salts (44) (about 40 cm-1) or platinum complexes (48) (105 cm-1). Often there is a correlation of the enthalpy of formation of complexes of ethylene to this frequency shift (44, 45). If we use the curve showing this correlation for heat of adsorption of ethylene on various molecular sieves (45), we find that a shift of 23 cm-1 should correspond to a heat of adsorption of 13.8 kcal. This value is in excellent agreement with the value of 14 kcal obtained for isosteric heats at low coverage. Thus, this comparison reinforces the conclusion that ethylene adsorbed on zinc oxide is best characterized as an olefin w-bonded to the surface, i.e., a surface w-complex. 

Synthesis and Properties of Alkyl, Alkenyl, Aryl, and Related Complexes of Silver 197... 

Synthesis, Properties, and Reactions of Carbene Complexes of Silver 203... 

Synthesis and Properties of Isocyanide and Carbonyl Complexes of Silver 221... 

Examples of silver(l) alkyl and alkenyl (including aryl) complexes have been known from as early as 1941 6-9 however, the number of examples is fairly limited with respect to that of the heavier congeners, copper(l) and gold(l). Such a phenomenon can readily be attributed to the relatively low stability of this class of complexes, both photochemically and thermally. Simple homoleptic alkyl and alkenyl complexes of silver(i) are known to be very unstable under ambient temperature and light, and successful isolation of this class is fairly limited and mainly confined to those involving perfluoroorganics.10 The structures and the metal-carbon bond-dissociation energies for... 

Li H, Michael Siu KW, Guevremont R, Le Blanc JCY (1997) Complexes of silver with peptides and proteins as produced in electrospray mass spectrometry. J Am Soc Mass Spectrom 8 781-792... 

On the other hand, complexes of silver can be used for calibration down to the silver ion activity, 10" m [142, 176]. 

Similar complexes of silver, copper and other metals are known. Some of them change colors on heating and are used in heat-sensitive paints and applied to machine parts made out of brass or iron ... 

Copper(I) and silver(I) complexes are exceptions of the general trend in stability constants with electron-donating or attracting substituents. Thus most known 7i-complexes of silver and copper are less stable than their respective ethylene complexes (154 156). The steric hindrance introduced by the substituents seems to have a major effect in those systems. 

Silver ion also catalyzes nucleophilic reactions of thiol esters, including reactions of acetylhomocysteine thiolactone (12) and diethylethylphosphonothiolate (52). In the first reaction, an insoluble complex of silver ion and the substrate was first produced at pH 7.5, which then reacted with the nucleophile, in this case an amino group of a protein. In the second reaction silver ion complexes of the substrate were also postulated, on the basis that silver ion complexes with sulfur are much more stable than those with oxygen (I). The complexes postulated were 1 1 and 2 1 silver ion-substrate complexes. These complexes were suggested to react with the nucleophiles, water and fluoride ion, giving as products phos-phonic acid and phosphonyl fluoride, respectively, and silver mercaptide. It is evident that the last reaction at least must involve only the direct interaction of a silver ion with the sulfur atom of the thiol ester without chelate formation. Therefore it appears the metal ion-catalyzed reactions of thiol esters are unique, in that they involve complex formation, but not chelate formation in their catalytic mechanism. 

Quadricovalent complexes of silver(II) should have the same planar configuration as those of copper(II). This has been verified33 for the silver(II) salt of picolinic acid, which is isomorphous with the cop-per(II) salt and which shows moreover the high birefringence expected for a parallel arrangement of planar molecules with the structure... 

Involvement of two nucleophilic nitrogen atoms is thus typical for the amino heterocycles. The mutual disposition of the pyridine and amine nitrogen atoms allows the formation of chelate structures for the cobalt complexes of purine, 221 and 222. Structures with the N, iV -five-membered metal cycles were proven for the tri- and tetranuclear complexes of silver ) with 8-aminoquinoline (223) (92IC4370), and polymeric copper- and rhodium-acetate clusters (224). Another coordination mode can be found in the complexes of 4-amino-3,5-bis(pyridin-2-yl)-l,2,4-triazole, (225 or... 

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