Copper complexes applications

Simultaneous detenuination of Cu and Zn in the form of coloured PAR complexes is performed at pH 10 in the presence of pyrophosphate which binds the admixtures of Al, Fe and Mn into the inactive complexes. The measurements of the change in the optical density are made at 520 and 550 nm before and after the destmction of the complexes by EDTA, or at 530 nm before and after the destruction of the copper complexes by the thioglycolic acid and the destmction of the zinc complexes by EDTA. The detection limit for Cu is 2-5, for Zn - 3 p.g/diW. The application of these methodics at pH 8 enables one to determine simultaneously Cu and Zn at high excess of the latter. 

The use of chiral bis(oxazoline) copper catalysts has also been often reported as an efficient and economic way to perform asymmetric hetero-Diels-Alder reactions of carbonyl compounds and imines with conjugated dienes [81], with the main focus on the application of this methodology towards the preparation of biologically valuable synthons [82]. Only some representative examples are listed below. For example, the copper complex 54 (Scheme 26) has been successfully involved in the catalytic hetero Diels-Alder reaction of a substituted cyclohexadiene with ethyl glyoxylate [83], a key step in the total synthesis of (i )-dihydroactinidiolide (Scheme 30). 

There are bi-, tri-, and tetradentate formazan dyes7 but only the tetradentate copper complex formazan dyes have found use as commercial products. The dye Cl Reactive Blue 160, of generic structure (41), is a representative example. Because of the intensity of their colors, the metal complex formazan dyes have also found application in analysis. Thus, the dye (42) detects zinc at a concentration of 1 part in 50 million.31... 

There has been great interest in Cu(II) as a result of its role in biology, and the versatility in its available radioactive isotopes. The chemistry of bis(thiosemicarbazonato) metal complexes has received much interest over the last decade with particular interest in the copper complexes that are known blood perfusion tracers and also display hypoxic selectivity. Biomedical applications revolve around its redox chemistry (12,83-88,98-104). 

Several copper enzymes will be discussed in detail in subsequent sections of this chapter. Information about major classes of copper enzymes, most of which will not be discussed, is collected in Table 5.1 as adapted from Chapter 14 of reference 49. Table 1 of reference 4 describes additional copper proteins such as the blue copper electron transfer proteins stellacyanin, amicyanin, auracyanin, rusticyanin, and so on. Nitrite reductase contains both normal and blue copper enzymes and facilitates the important biological reaction NO) — NO. Solomon s Chemical Reviews article4 contains extensive information on ligand field theory in relation to ground-state electronic properties of copper complexes and the application of... 

The only copper complexes of tridentate azo compounds are 1 1 structures, since copper(II) has a CN of 4. They can be prepared by the reaction of the azo compound with a copper(II) salt in an aqueous medium at 60 °C. The major application for copper-complex azo dyes is as direct or reactive dyes for the dyeing of cellulosic fibres. They are seldom developed for use on wool or nylon, although various orange and red 1 1 copper-complex azopyrazolones (5.42) were synthesised recently and evaluated on these fibres by application from a weakly acidic dyebath [24]. 

Special consideration should be paid to metal complexes such as azomethine pigments (Sec. 2.10). At high temperatures, the yellow copper complex with the chemical constitution 10, incorporated in PVC, will exchange its chelated copper atoms with the metal atoms present in the application medium. Stabilizers containing barium/cadmium or lead produce yellow shades, while dibutyl tin thiogly-colate or other tin compounds produce a brilliant medium red. Color change is slow at low temperatures, but at 160°C the effect is rapid [108],... 

Chiral dirhodium(II) carboxamidates are preferred for intramolecular cyclopropanation of allylic and homoallylic diazoacetates (Eq. 2). The catalyst of choice is Rh2(MEPY)4 when R " and R are H, but Rh2(MPPIM)4 gives the highest selectivities when these substituents are alkyl or aryl. Representative examples of the applications of these catalysts are listed in Scheme 15.1 according to the cyclopropane synthesized. Use of the catalyst with mirror image chirality produces the enantiomeric cyclopropane with the same enantiomeric excess [33]. Enantioselectivities fall off to a level of 40-70% ee when n is increased beyond 2 and up to 8 (Eq. 2) [32], and in these cases the use of the chiral bisoxazoline-copper complexes is advantageous. 

The widespread application and development of dithiophosphate esters have far outdistanced efforts to provide methods for the analysis of such materials. For ETHION (2) Graham has shown that it is possible to analyze for the ester by hydrolyzing it in the presence of copper (II) ion and then determining the amount of the copper complex qpec-trophotometrically. A yellow copper complex similarly formed with MALATHION serves... 

Chromium and cobalt are the metals most commonly used in dyestuffs for polyamide fibres and leather because of their kinetic inertness and the stability of their complexes towards acid. Since the advent of fibre-reactive dyestuffs, chromium and cobalt complexes have also found application as dyestuffs for cellulosic fibres, particularly as black shades of high light-fastness. Copper complexes are of more importance as dyes for cellulosic fibres and are unsuitable for polyamide fibres because of their rather low stability towards acid treatments. 

The most important azo compounds employed in the manufacture of dyes of this type are those containing the < ,o -dihydroxyazo-, the o-hydroxy-o -carboxyazo- and the o-hydroxy-o -amino-diarylazo systems. It is well established3 33-0 that these form four-coordinate copper and nickel complexes (35) in which the coordination sphere of the metal can be completed by a variety of neutral ligands. In both cases the light-fastness of the parent azo compound is improved as a result of complex formation but the nickel complexes are insufficiently stable towards acid to be of commercial interest as dyestuffs. The history of copper complexes has already been discussed (Section 58.1) and will not be considered further here, although it is worthy of mention that currently the most important copper complex dyestuffs are those containing fibre-reactive systems, e.g. (36), for application on cellulosic fibres. 

The preparation of chromium(III) and cobalt(III) complexes of tetradentate formazans in which the coordination sphere of the metal is completed by a variety of neutral ligands has been reported116 and these (185) were claimed to be very stable towards acids. By analogy with copper complexes, however, some doubt must exist regarding the structures assigned to those complexes derived from l,5-bis(2-carboxyphenyl)formazans. Various dyestuff and pigment applications have... 

The applications of copper complexes are extremely varied and of great importance. Many of them are relevant to other chapters of this volume. Of those pertaining to this chapter, the two most important areas are polymer additives and, particularly, fungicides. The latter may be divided into four main areas crop protection, the protection of wood and that of cotton, and their use in antifouling paints. 

The analytical application of MPA-Gly-Gly-His modified electrodes was also demonstrated in the determination of Cu2+ in lake water. The concentration of Cu2+ in lake water, after dilutions were accounted for, was ll+4nM (95% confidence interval). The analytical result obtained is significantly lower than that measured by ICP-MS of 925 + 22nM (95% confidence interval). This difference is more pronounced in lake water compared to tap water presumably due to greater presence of copper complexes in lake water which are not measured by the MPA-Gly-Gly-His sensor. 

Shuman, M.S. and Michael, L.C., 1978. Application of the rotated disk electrode to measurement of copper complex dissociation rate constants in marine coastal samples. Environm. Sci. Technol., 12 1069-1072. 

Van den Berg, C.M.G., 1982. Determination of copper complexation with natural organic ligands in seawater by equilibration with Mn02- II. Experimental procedures and application to surface seawater. Mar. Chem., 11 323-342. 

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