Copper II Salts

Copper(II) salts (blue in aqueous solution) are typical M(II) salts but generally have a distorted co-ordination (Jahn-Teller distortion, 4 near plus 2 far neighbours). Extensive ranges of complexes are known, particularly with /V-ligands. 

Copper Il) sulphide, CuS. Black solid, Cu plus excess S or copper(II) salt plus H2S. Decomposes to copper(l) sulphide, CU2S, on heating. 

In the presence of excess iodide ions, copper(II) salts produce the white insoluble copper(I) iodide and free iodine, because copper(II) oxidises iodide under these conditions. The redox potential for the half-reaction ... 

Hydrated copper(ll) hydroxide, Cu(OH)2, is precipitated as a pale blue solid when alkali is added to an aqueous solution of a copper(II) salt ... 

The normal carbonate CuCOj is not known two naturalls occurring basic carbonates have already been mentioned. If a solution of, for example, sodium carbonate is added to a solution of a copper(II) salt, a green basic carbonate is precipitated the reactions are ... 

When a copper(II) salt dissolves in water, the complex aquo-ion [Cu(H2p)6P is formed this has a distorted octahedral (tetragonal) structure, with four near water molecules in a square plane around the copper and two far water molecules, one above and one below this plane. Addition of excess ammonia replaces only the four planar water molecules, to give the deep blue complex [Cu(NH3)4(H20)2] (often written as [Cu(NHj)4] for simplicity). TTo obtain [Cu(NH3)6], water must be absent, and an anhydrous copper(II) salt must be treated with liquid ammonia. 

Copperil) oxide, CujO, occurs naturally as the red cuprite. It is obtained as an orange-yellow precipitate by the reduction of a copper(II) salt in alkaline solution by a mild reducing agent, for example glucose, hydroxylamine or sodium sulphite ... 

Copperil) cyanide. CuCN (and copperil) thiocyanate), are similarly obtained as white precipitates on adding cyanide and thiocyanate ions (not in excess) respectively to copper(II) salts ... 

Irradiation of 3,5-disubstituted isoxazoles in alcoholic solvents gave reaction products such as acetals incorporating the reaction solvent. The use of triethylamine in acetonitrile media produced ketene-aminals by reductive ring cleavage. The reductive ring cleavage product was also obtained by irradiation of the isoxazole in alcohol in the presence of copper(II) salts (Scheme 3) (76JCS(P1)783). 

This synthesis is only one example of a wide range of reactions which involve aryl (or alkyl) radical addition to electron-deficient double bonds resulting in reduction.The corresponding oxidative reaction using aryl radicals is the well known Meerwein reaction, which uses copper(II) salts. 

Hence 0.771 - 0.059161og,o(10 ) = 0.771 - 1.301 = -0.530 V Thus by making the solution alkaline the sign of has been reversed and the susceptibility of Fe (aq) to oxidation (i.e. its reducing power) enormously increased. This is why white, precipitated Fe(OH)2 and FeCOs are rapidly darkened by aerial oxidation and why Fe in alkaline solution will reduce nitrates to ammonia and copper(II) salts to metallic copper. 

The Glaser coupling reaction is carried out in aqueous ammonia or an alcohol/ammonia solution in the presence of catalytic amounts of a copper-I salt. The required copper-II species for reaction with the acetylide anion R-C=C are generated by reaction with an oxidant—usually molecular oxygen. For the Eglinton procedure, equimolar amounts of a copper-II salt are used in the presence of pyridine as base. 

Cupri-. cupric, copper(II). -azetst, n. cupric acetate, copper(II) acetate, -carbonat, n. cupric carbonate, copper(II) carbonate, -chlorid, n. cupric chloride, copper(II) chloride. -hydroxyd, n. cupric hydroxide, cop-per(II) hydroxide. -ion, n. cupric ion, copper(II) ion. -ozalat, n. cupric oxalate, copper(II) oxalate, -oxyd, n. cupric oxide, copper(II) oxide. -salz, n. cupric salt, copper(II) salt, -suifat, n. cupric sulfate. copper(II) sulfate, -sulfid, n. cupric sulfide, copper(II) sulfide, -verbihdung, /. cupric compound, copper(II) compound, -wein-saure, /. cupritartaric acid. 

Kupferoxyd, n. cupric oxide, copper(II) oxide, -ammoniak, n. ammoniacal copper oxide, cu-prammonium. -ammoniakkunstseide, -am-moniakzellulose, /. cuprammonium rayon, -hydrat, n. cupric hydroxide, copper(II) hydroxide. -salz, n. cupric salt, copper(II) salt. 

The first partial chiral resolution reported in CCC dates from 1982 [120]. The separation of the two enantiomers of norephedrine was partially achieved, in almost 4 days, using (/ ,/ )-di-5-nonyltartrate as a chiral selector in the organic stationary phase. In 1984, the complete resolution of d,l-isoleucine was described, with N-dodecyl-L-proline as a selector in a two-phase buffered n-butanol/water system containing a copper (II) salt, in approximately 2 days [121]. A few partial resolutions of amino acids and dmg enantiomers with proteic selectors were also published [122, 123]. 

When ammonia is added to an aqueous solution of a copper(II) salt, a deep, almost opaque, blue color develops (Figure 15.1). This color is due to the formation of the Cu(NH3)42+ ion, in which four NH3 molecules are bonded to a central Cu2+ ion. The formation of this species can be represented by the equation... 

Treatment of 4-substituted phthalimides with a copper(II) salt, urea, and ammonium molyb-date(VI) yields phthalocyanines 5.407 Again, structural isomers are obtained. 

The predominant gaseous products of the decomposition [1108] of copper maleate at 443—613 K and copper fumarate at 443—653 K were C02 and ethylene. The very rapid temperature rise resulting from laser heating [1108] is thought to result in simultaneous decarboxylation to form acetylene via the intermediate —CH=CH—. Preliminary isothermal measurements [487] for both these solid reactants (and including also copper malonate) found the occurrence of an initial acceleratory process, ascribed to a nucleation and growth reaction. Thereafter, there was a discontinuous diminution in rate (a 0.4), ascribed to the deposition of carbon at the active surfaces of growing copper nuclei. Bassi and Kalsi [1282] report that the isothermal decomposition of copper(II) adipate at 483—503 K obeyed the Prout—Tompkins equation [eqn. (9)] with E = 191 kJ mole-1. Studies of the isothermal decompositions of the copper(II) salts of benzoic, salicylic and malonic acids are also cited in this article. 

Copper proteins, 1,168 5,720 models, 2,85 nonblue, 5,723 type 111, 5,724 Copper salts cellulose dyes, 6,38 Copper(I) salts stabilization, 6,786 Copper(II) salts ammoniacal leaching, 6,787 oxidant... 

Potassium peroxodisulphate (K2S2Og) also oxidizes sulphoxides to sulphones in high yield, either by catalysis with silver(I) or copper(II) salts at room temperature85 or in pH 8 buffer at 60-80 °c86-88. The latter conditions have been the subject of a kinetic study, and of the five mechanisms suggested, one has been shown to fit the experimental data best. Thus, the reaction involves the heterolytic cleavage of the peroxodisulphate to sulphur... 

High yields of sulphoximines are also obtained from the reaction of sulphoxides with chloramine-T in the presence of copper(II) salts or copper metal (equation 68)180,184. 

Partial hydrolysis of a potentially heptadentate Schiff-base tripodal ligand derived from tris-(2-aminoethyl)amine and 2-hydroxyacetophenone, induced by copper(II) salts, was reported and the final copper(II) complex (377) was characterized.333 Using salicylaldehyde as a co-ligand, with a copper(II) complex (378), catalytic epoxidation was demonstrated 334... 

Buffinger, D. R., et al J. Coord. Chem., 1988, 19(1-3), 197 A double salt of the nitrate and the copper(II) salt of an organometallic ligand was found to explode at around 100°C. In view of the oxidising powers of the nitrate, complexes of this nature are not likely to be stable. 

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