Silver complex compounds, with

Other polydentate ligands are polyamines and related ligands. Stability constants of silver(I) complexes with polyamines in dimethyl sulfoxide,419 A-methyl-substituted 4-methyldiethylene-triamines,420 or ethylene- or N- or C-methylated ethylenediamine in aqueous solution have been reported.421 The structure of the silver 1,3-diaminopropane complex, [Ag NH2(CH2)3NH2 ]-C104,422 and complex formation with 1,4-diaminobutane and 1,5-diaminopentane have been reported.423 A dinuclear silver(I) compound with ethylenediamine [(enH)Ag(en)Ag(enH)2]4+ has... 

USE Forms a complex compound with ferrous ions which is used under the name of Terrain as an indicator in oxidation reduction systems, eg., titration of ferrous salts. Also used in determination of nickel, ruthenium, silver and other metals. 

Valuable tests for the indentification of the halogens depend upon the insolubility of the silver halides and their relative tendencies to form soluble complex compounds with ammonia. 

Stable olefin complexes of metals containing fewer than two d electrons are not known. Complexes possessing d and d" electronic structures are numerous. In the case of [Ag(C2H4)] , it can be expected that the n back-bonding is not as important as in the Pt(II) complexes. This was confirmed by ab initio calculations carried out for the silver compound. They show that the most essential changes in the electronic structure of ethylene in the silver complex are caused by polarization effects which are induced by the positive charge of the silver atom. The olefin-metal bonding orbital has only 6.5% contribution of the 5 Ag orbital. This result was confirmed by ESR measurements carried out for olefin silver complexes irradiated with y-rays. Based on... 

Silver and sulfur combine even in the cold to form silver sulfide. The tendency of silver to tarnish is an example of the ease with which silver and sulfur compounds react. PoHshes that contain silver complexing agents, such as chloride ion or thiourea, are used to remove silver tarnish. 

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... 

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). 

Silver(III) Compounds. No simple silver(Ill) compounds exist. When mixtures of potassium or cesium haUdes are heated with silver hahdes ia a stream of fluorine gas, yellow KAgF [23739-18-6] or CsAgF [53585-89-0] respectively, are obtained. These compounds are diamagnetic and extremely sensitive to moisture (21). When Ag2S04 is treated with aqueous potassium persulfate ia the presence of ethylenedibiguanidinium sulfate, the relatively stable Ag(Ill)-ethylenebiguanide complex is formed. 

Release by Silver-Assisted Cleavag e. A soluble silver complex formed imagewise in the undeveloped areas of the silver haUde layer may be used to effect a cleavage reaction that releases a dye or a dye precursor. The process yields positive dye transfer images directiy with negative-working emulsions (46). An example is the silver-assisted cleavage of a dye-substituted thiazolidine compound, as shown in equation 7. 

Isatin (190) is a compound with interesting chemistry. It can be iV-acetylated with acetic anhydride, iV-methylated via its sodium or potassium salt and O-methylated via its silver salt. Oxidation of isatins with hydrogen peroxide in methanolic sodium methoxide yields methyl anthranilates (81AG(E)882>. In moist air, O-methylisatin (191) forms methylisatoid (192). Isatin forms normal carbonyl derivatives (193) with ketonic reagents such as hydroxylamine and phenylhydrazine and the reactive 3-carbonyl group also undergoes aldol condensation with active methylene compounds. Isatin forms a complex derivative, isamic acid (194), with ammonia (76JCS(P1)2004). 

All three M+ ions are known to form compounds with the unusual digonal linear coordination (see also section 4.9.7), though this is most common for gold. As a result, complexes R3PMX of copper and silver are normally di-and tetranuclear species with 3- or 4-coordinate metals, while the gold analogues are 2-coordinate monomers. This is the reverse of what would be expected on steric grounds [13, 14],... 

The fact that pentacarbonyl carbene complexes react with enynes in a chemo-selective and regiospecific way at the alkyne functionality was successfully applied in the total synthesis of vitamins of the Kj and K2 series [58]. Oxidation of the intermediate tricarbonyl(dihydrovitamin K) chromium complexes with silver oxide afforded the desired naphthoquinone-based vitamin K compounds 65. Compared to customary strategies, the benzannulation reaction proved to be superior as it avoids conditions favouring (E)/(Z)-isomerisation within the allylic side chain. The basic representative vitamin K3 (menadione) 66 was synthesised in a straightforward manner from pentacarbonyl carbene complex 1 and propyne (Scheme 38). 

Attempts to oxidise silver dithiocarbamato complexes with halogens to compounds with the metal in higher oxidation states obviously failed. By addition of iodine to a solution of [Ag(Bu2 fc)]g in CHQ3, an insoluble product is formed with the composition rjA% S> X2dtc) 141). With other alkyl groups similar complexes are obtained. Investigations about the nature of this type of compounds are in progress. 

Oxidation of the complexes [Ag(Py)4][MoF6] and [Ag(Py)2][UF6] in acetonitrile by MoF6 and UF6, respectively, leads to the silver(III) compounds [Ag(Py)4(NCMe)][MoF6]3 and [Ag(Py)2(NC-Me)3][UF6]3, which are strong oxidizing agents.167 Other pyridine silver(III) complexes have been obtained by oxidation of silver nitrate and ammonia with ammonium peroxydisulfate in aqueous... 

The reaction of A-benzyl-C-imidazolyllithium with [Ag(N03)(SMe)2] affords the corresponding C-imidazolylsilver (Equation (3)), which has been proposed by molecular weight determination to be trimeric.297 A-Functionalized C-imidazolylsilver compounds or carbene-type silver complexes are obtained by reaction of the imidazolium salt with Ag20 or Ag2C03 some of these are shown in Figure 4 298,299... 

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