Metallic salts preparation using exchange reactions

The preparation of water-miscible ionic liquids can be a more demanding process, as the separation of the desired and undesired salts may be complex. The use of silver salts described above allows the preparation of many salts in very high purity, but is clearly too expensive for large-scale use. As a result, a number of alternative protocols have been developed that employ cheaper salts for the metathesis reaction. The most common approach remains to carry out the exchange in aqueous solution using either the free acid of the appropriate anion, the ammonium salt, or an alkali metal salt. When using this approach, it is important that the desired ionic liquid can be isolated without excess contamination from unwanted halide-... 

In a separate series of experiments the speciation of niobium was studied using exchange reactions of metallic niobium with bismuth, silver or nickel ions in NaCl-KCl melts. The starting NaCl-KCl-BiC melt was prepared by chlorinating bismuth metal (>98%, Reahim) by chlorine gas in the molten salt mixture. Nickel and silver chloride-containing melts were prepared by dissolving anhydrous nickel chloride (98%, Aldrich) and silver chloride (99%, Aldrich), respectively, in NaCl-KCl with HCl gas bubbled through the electrolyte for 2 h to eliminate traces of absorbed moisture. 

The exchange of lithium in a dililhium phthalocyanine is a useful tool to prepare metal (e.g., zinc) or metal-free phthalocyanines. For this purpose, the dilithium phthalocyanine is prepared by reaction of phthalonitrile and lithium alkoxide in an alcohol, e.g. pentan-l-ol. In most cases, the lithium phthalocyanine is not separated but directly converted into the respective phthalocyanine by treatment with metal salts or, in the case of metal-free phthalocyanine, with acid or water. 

Solid-state metathesis reactions. For a number of compounds, solid-state metathesis (exchange) reactions have the advantages of a rapid high-yield method that starts from room-temperature solids and needs little equipment. The principle behind these reactions is to use the exothermicity of formation of a salt to rapidly produce a compound. We may say that for instance a metal halide is combined with an alkali (or alkaline earth) compound of a /7-block element to produce the wanted product together with a salt which is then washed away with water or alcohol. Metathesis reactions have been used successfully in the preparation of several crystalline refractory materials such as borides, chalcogenides, nitrides. 

There are several useful means for preparation of organomercury compounds. The general metal-metal exchange reaction between mercury(II) salts and organolithium or magnesium compounds is applicable. The oxymercuration reaction discussed in Section... 

Preparation of Metal Sulphides by an Exchange Decomposition Reaction. Precipitation with Ammonium Sulphide. Pour 2 ml each of solutions of iron(ll), manganese(II), zinc, cadmium, lead, antimony, and copper salts into separate test tubes. Add 2 ml of an ammonium sulphide solution to each tube. Note the colour of the formed precipitates. Write the equations of the reactions and the values of the solubility products of the sulphides of these metals (see Appendix 1, Table 12). Using the concept of the solubility product, explain the process of precipitation of sulphides under these conditions. 

The complications which result from the hydrolysis of alkali metal cyanides in aqueous media may be avoided by the use of non-aqueous solvents. The one most often employed is liquid ammonia, in which derivatives of some of the lanthanides and of titanium(III) may be obtained from the metal halides and cyanide.13 By addition of potassium as reductant, complexes of cobalt(O), nickel(O), titanium(II) and titanium(III) may be prepared and a complex of zirconium(0) has been obtained in a remarkable disproportion of zirconium(III) into zirconium(IV) and zirconium(0).14 Other solvents which have been shown to be suitable for halide-cyanide exchange reactions include ethanol, methanol, tetrahydrofuran, dimethyl sulfoxide and dimethylformamide. With their aid, species of different stoichiometry from those isolated from aqueous media can sometimes be made [Hg(CN)3], for example, is obtained as its cesium salt form CsF, KCN and Hg(CN)2 in ethanol.15... 

Complex compounds with halide bridges are prepared by immediate interaction of unsaturated hydrocarbons with metal salts (Sec. 2.2.4.1). Their examples are classic 7i-complexes of the type 123 which are characteristic for fi 8-metals [75]. Such complexes are also formed by the method of ligand exchange. The bridges of this type are widespread in products of cyclometallation reactions with the use of metal halides (Sec. 2.2.5.1) 371-374, 381, 382 [41,46,48]. An example of such a synthesis is the reaction of arylhydrazones of 2-oxopropionic aldehyde and benzoylformalde-hyde, as well as butadiene-2,3-dione 635, with palladium dichloride, leading (3.71) to dipalladium complexes 636 [88] ... 

The preparation of organopalladium compounds by exchange reactions of palladium salts and organo-lead, -tin, or -mercury compounds is apparently not the only way that they can be obtained but it does seem to be the most useful way. Convincing evidence is now available to show that direct metalation of aromatic compounds with palladium salts (palladation) can occur. Since the initial report of Cope and Siekman 32> that palladium chloride reacted readily with azobenzene to form an isolable chelated, sigma-bonded arylpalladium compound, several additional chelated arylpalladium compounds have been prepared. 

Hydrated oxides with clearly exhibited basic and acidic properties are well soluble in water. They are prepared by the interaction of the corresponding oxides or metals with water. Weak bases, ampholytes and weak acids are practically insoluble or poorly soluble. Exchange reactions between the solutions of the corresponding salts and strong bases are used to synthesize them. 

This reaction is analogous to the preparation of bis(4-imino-2-pentanonato)copper(II) [bis(4-amino-3-penten-2-onato)copper(II)] described by Holtzclaw, Collman, and Alire, and it consists in mixing an ethanolic solution of the -keto imine ( -imino ketone) with an ammoniacal metal salt solution. Advantages of this technique are the simplicity of preparation and the fact that acetylacetone imide (4-imino-2-pentanone) can be purchased. The product is useful as a starting material in ligand-exchange reactions. 

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