Salt/complex formation

Just as the dissolution of ionic salts in a solvent system requires that the solvation energy of the ions in solution overcome the lattice energy of the ionic salt, similarly,polymer-metal salt complex formation proceeds,provided the polymer matrix effectively solvates the ions and overcomes the lattice energy of the ionic salt. Three essential criteria for this process have been identified [37] ... 

While oxygen-containing polymers have received more attention other heteroatom-containing polymers have also been studied. In addition to homopolymers, copolymers containing more than one monomer has also received attention. Further, modifications of homopolymers by plasticizers, or crosslinking, or grafting to improve the properties of the polymers towards polymer-salt complex formation or increasing the dimensional stability of the materials has also been a focus of research. 

Extraction of uncharged species into organic media by onium salts. These include transition metal salts (complex formation with, e.g. CuX, PdCy, and acids, H2O2 and amines which form weakly hydrogen-bonded complexes with quats... 

Allylic amine is a less reactive leaving group[7], but the allylic ammonium salts 214 (quaternary ammonium salts) can be used for allylalion(l30,131]. Allylic sulfonium salts are also used for the allylation[130]. The allylic nitrile in the cyclic aminonitrile 215 can be displaced probably via x-allylic complex formation. The possibility of the formation of the dihydropyridinium salts 216 and subsequent conjugate addition are less likelyfl 32],... 

Single-Stack Acceptor. Simple charge-transfer salts formed from the planar acceptor TCNQ have a stacked arrangement with the TCNQ units facing each other (intermolecular distances of ca 0.3 nm (- 3). Complex salts of TCNQ such as TEA(TCNQ)2 consist of stacks of parallel TCNQ molecules, with cation sites between the stacks (17). The interatomic distance between TCNQ units is not always uniform in these salts, and formation of TCNQ dimers (as in TEA(TCNQ)2) and trimers (as in Cs2(TCNQ)Q can lead to complex crystal stmctures for the chainlike salts. 

The lanthanides form many compounds with organic ligands. Some of these compounds ate water-soluble, others oil-soluble. Water-soluble compounds have been used extensively for rare-earth separation by ion exchange (qv), for example, complexes form with citric acid, ethylenediaminetetraacetic acid (EDTA), and hydroxyethylethylenediaminetriacetic acid (HEEDTA) (see Chelating agents). The complex formation is pH-dependent. Oil-soluble compounds ate used extensively in the industrial separation of rate earths by tiquid—tiquid extraction. The preferred extractants ate catboxyhc acids, otganophosphoms acids and esters, and tetraaLkylammonium salts. 

For deliming, ammonium salts and acids are used. The proportion of ammonium salts to acids and the type of acids employed is a matter of the tanner s choice. The acid neutralizes the lime, Ca(OH)2, thereby adjusting the pH. The ammonium salts have two functions to buffer the solution to a pH required for bating, and to form calcium ammonium complexes. The acidity and the complex formation solubilize the calcium and serve to bring the hide to the desired pH. 

Only three simple silver salts, ie, the fluoride, nitrate, and perchlorate, are soluble to the extent of at least one mole per Hter. Silver acetate, chlorate, nitrite, and sulfate are considered to be moderately soluble. AH other silver salts are, at most, spatingly soluble the sulfide is one of the most iasoluble salts known. SHver(I) also forms stable complexes with excess ammonia, cyanide, thiosulfate, and the haUdes. Complex formation often results ia the solubilization of otherwise iasoluble salts. Silver bromide and iodide are colored, although the respective ions are colorless. This is considered to be evidence of the partially covalent nature of these salts. 

Interaction of iron(II) chloride with the lithium salt of R4B2NJ (R = Me, Et) gives sandwiches 61 (R = Me, Et) (67ZAAC1, 96MI4), resembling in electronic properties those of ferrocene (99ICA(288)17). The n- rf-) complex stems from the further complex-formation of 61 (R = Me, Et) with mercury(II) salts via the unsubstituted nitrogen atom. 

Mino and Kaizerman [12] established that certain. ceric salts such as the nitrate and sulphate form very effective redox systems in the presence of organic reducing agents such as alcohols, thiols, glycols, aldehyde, and amines. Duke and coworkers [14,15] suggested the formation of an intermediate complex between the substrate and ceric ion, which subsequently is disproportionate to a free radical species. Evidence of complex formation between Ce(IV) and cellulose has been studied by several investigators [16-19]. Using alcohol the reaction can be written as follows ... 

Ethylenediaminetetra-acetic acid, largely as the disodium salt of EDTA, is a very important reagent for complex formation titrations and has become one of the most important reagents used in titrimetric analysis. Equivalence point detection by the use of metal-ion indicators has greatly enhanced its value in titrimetry. 

By Production of Azepinium Salts, Protonation, Complex Formation and Alkylation... 

Kuokkanen (1986, 1987 a, 1991) supported the proposal of Nakazumi et al. (1983) based on kinetic and spectrophotometric comparisons of arenediazonium salt solutions in the presence of 18-crown-6 and pentaglyme. He also extended the systematic work on complex formation of benzenediazonium salts, substituted in the 2-position, and in the presence of 15-crown-5 (Kuokkanen, 1990 Kuokkanen et al, 1991). He discovered a useful way to differentiate between the two types of complexes in Scheme 11-2. Increasing the relative concentration of the host compound shifts the ultraviolet absorption band of both types of complex hypsochromically, whereas the NN stretching frequencies are significantly increased only in the case of insertion complexes. ... 

Racemic mixtures of sulfoxides have often been separated completely or partially into the enantiomers. Various resolution techniques have been used, but the most important method has been via diastereomeric salt formation. Recently, resolution via complex formation between sulfoxides and homochiral compounds has been demonstrated and will likely prove of increasing importance as a method of separating enantiomers. Preparative liquid chromatography on chiral columns may also prove increasingly important it already is very useful on an analytical scale for the determination of enantiomeric purity. 

A subdivision similar to that for sulphones has been adopted oxidation methods reduction methods methods dependent on basic properties complex formation with inorganic salts spectroscopy chromatography. 

The sites for complex formation in DMSO with inorganic salts depend remarkably on the nature of the metals involved in the salts. The alkali or alkali earth metallic salts form a complex with the oxygen atom in DMSO while Pd(II) or Pt(II) associates strongly at the sulphur atom. The IR frequency of the S—O bond of DMSO shifts to even lower wave numbers when associated with such metal cations as Li+, Na+ or Ca+ +34. On the other hand, in the case of Pd(II) or Pt(II), the S—O frequency appears at higher wave numbers, at around llOO-llAOcm 135. These different shifts for the S—O frequency afford a convenient diagnosis to determine whether the cation associates with the oxygen or the sulphur atom in DMSO. 

To treat complex formation quantitatively, we note that complex formation and the dissolving of the salt are both at equilibrium so we can write... 

---