Acetonitrile metal dissolution

POMs form by a self-assembly process, typically in an acidic aqueous solution and can be isolated as powder or crystals with counter-cations. Appropriate selection of counter-cations can control the solubility of POMs in various reaction media. For homogeneous system, alkylammonium cations, generally TBA, are selected as counter-cations of POM anions for the dissolution in organic solvents such as acetonitrile, DMF, DMSO and 1,2-dichloroethane. POMs with metal counter-cations such asNa +, K+,Rb+,Cs + and Ag + are not soluble in common organic solvents. 

The electrochemical dissolution of copper and other metals (see Sec. 3.4.2 on direct electrosynthesis), in solutions of tetramethylthiuram disulfide and its analogues in nonaqueous solutions of acetone and acetonitrile, was first carried out by Tuck and coworkers [619]. Complexes with a general formula given by M(R2NCS2) are formed with good yields under these conditions. The proposed mechanism... 

Since the polymer and the metal salt involved are both solid materials, the preparation of a polymer salt complex is achieved by the dissolution of the two materials in a common solvent such as acetonitrile, methanol or THF followed by a slow removal of the solvent in vacuum. This results in either the bulk polymer-metal salt complex or a thin film depending upon the method of preparation. It is essential to ensure that no traces of moisture are present and hence the operations are carried out by using Schlenk techniques or glove box methods. The essential reaction that occurs in the formation of a polymer-metal salt complex can be written as... 

Au(Cr)-covered crystals were used in nonaqueous solutions (e.g., butanol [111] or acetonitrile [158]), anodic oxidation of chromium was not observed. When Ti was used instead of Cr as the adhesion-promoting layer, dissolution of this metal through gold was very slow. Long-term use of Au(Ti) coatings shows that Ti also disappears, but the adhesion of gold to the resonator surface remains as before. 

C0CI2 effected the replacement of one and two iron centers in the triiron core with cobalt to generate (L )CoFe2Cl(CH3CN) and (L )Co2FeCl(CH3CN), respectively (Scheme 8.7). The reaction was performed in THF at rt for 3 h, and the dissolution of the reaction crude into acetonitrile resulted in the precipitation of the acetonitrUe-cluster adducts as a crystalline material. Notably, no metal atom substitution occurs at the unique iron site, where chloride is bound. 

The electrochemical behavior of the crystalline fullerene films is also influenced by the medium. Dissolution of the reduced films is quite important for the films doped with small cations in acetonitrile. It is significantly reduced for large tetraalkylammonium cations or especially so for the polypyridine complex metal cations in acetonitrile, probably because of relatively high polarizability of the aromatic ligands and fullerene anions in the latter case. The extent of dissolution is also a function of the extent of film reduction (see Table 7.9). For solid polymer electrolytes (see refs. [165,167]), the polymer may take part in the... 

For example, to prepare [In(DMAA)6][C104]3, In(C104)3 is dissolved in dimethylacetamide. The resulting compound is isolated as a solid by removal of excess solvent.33 The salt, [Ag(DMF)2lIN03], is prepared in a similar manner by dissolution of silver nitrate in DMF followed by isolation of the product as a solid by the addition of benzene.34 On dissolution of Cu(BF4)2 in acetonitrile in the presence of metallic copper as a reductant, [Cu(MeCN)4][BF4] is formed.35... 

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