Mixed copper complexes

There have also been examples of ligand-exchange CSPs. Schmid et al. [159] used a ligand-exchange monomer as a chiral selector. The chiral selector, monomer, cross-linker, and charged monomer were polymerized to produce monolithic capillaries capable of chiral recognition and generation of EOF. The separation is achieved due to the differences in the stability between the ternary mixed copper complexes formed by the enantiomers and the CSP. 

Crystal stmctures of complexes of copper(II) with aromatic amine ligands and -amino acids " " and dipeptides" have been published. The stmctures of mixed ligand-copper complexes of L-tryptophan in combination with 1,10-phenanthroline and 2,2 -bipyridine and L-tyrosine in combination with 2,2 -bipyridine are shown in Figure 3.2. Note the subtle difference between the orientation of the indole ring in the two 1,10-phenanthroline complexes. The distance between the two... 

Sodium copper chlorophyllin, approved by the FDA as a color additive in citrus-based dry beverage mixes, should have a ratio of absorbance (SoretQ band) not less than 3.4 and not more than 3.9. In Europe, purity criteria of the food additives E141[i] and E141[ii], which are copper complexes of chlorophyll and chlorophyllin, respectively, are set out in the EC color specifications that include identification and spectrophotometric assay tests. ... 

Mixed copper sulphide oxide ores. These contain varieties of both sulphide and oxide minerals, and are the most complex copper-bearing ores from a beneficiation point of view. The major copper minerals present in this ore type include bomite, chalcocite, covellite, malachite, cuprite and chrysocolla. In some cases, significant amounts of cobalt minerals are also present in this ore. 

The complexation of anionic species by tetra-bridged phosphorylated cavitands concerns mainly the work of Puddephatt et al. who described the selective complexation of halides by the tetra-copper and tetra-silver complexes of 2 (see Scheme 17). The complexes are size selective hosts for halide anions and it was demonstrated that in the copper complex, iodide is preferred over chloride. Iodide is large enough to bridge the four copper atoms but chloride is too small and can coordinate only to three of them to form the [2-Cu4(yU-Cl)4(yU3-Cl)] complex so that in a mixed iodide-chloride complex, iodide is preferentially encapsulated inside the cavity. In the [2-Ag4(//-Cl)4(yU4-Cl)] silver complex, the larger size of the Ag(I) atom allowed the inner chloride atom to bind with the four silver atoms. The X-ray crystal structure of the complexes revealed that one Y halide ion is encapsulated in the center of the cavity and bound to 3 copper atoms in [2-Cu4(//-Cl)4(//3-Cl)] (Y=C1) [45] or to 4 copper atoms in [2-Cu4(/U-Cl)4(/U4-I)] (Y=I) and to 4 silver atoms in [2-Ag4(/i-Cl)4(/i4-Cl)] [47]. NMR studies in solution of the inclusion process showed that multiple coordination types take place in the supramolecular complexes. 

In a mixed copper-zinc solution of complex cyanide, however, the Cu ion concentration can be reduced to the order of lO mol/L and the concentration ratio (zinc ion)/(copper ion) will be made very large. A detailed calculation for this case is given by Faust in the 1974 edition of Modem Electroplating (1). It is shown there, and in detail below, that the copper cyanide complex is Cu(CN)3 , for which the dissociation value is known. The dissociation constant for the zinc cyanide complex, Zn(CN)4 , is also well known. Using those values that determine the fraction concentration of the free metal ion in solution and assuming an initial specific molar concentration, it is shown below that their respective reversible electrode potentials [see also Eq. (11.1)] can be brought together. 

The other copper-only binuclear centre to be considered is the CuA or purple copper complex. It is part of the terminal oxidase in mitochondrial respiration, cytochrome c oxidase (COX). Its EPR signature, a seven-line spectrum, has since long been known to be different from the classes type 1 to 3 and arises from two copper ions in a 1.5 valence (or mixed valence) state, first proposed from EPR-analysis of a similar center in nitrous oxide (N20) reductase. There is a close correspondence between the blue and purple states of copper since each of the two copper ions in CuA can be considered as being structurally related to the mononuclear blue site coordination. 

Table 17 The Robin and Day Classification of Mixed Valence Complexes of the Copper(I) and (II) Ions340 362... 

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