Copper chloride complexes with

Copper Chloride Complexes with Poly(2-vinylpyridine)... 

Archer C, Vance D (2002) Large fractionation in Fe, Cu and Zn isotopes associated with Archean microhially-mediated sulphides (abstr.). Geochim Cosmochim Acta (suppl.) 66 A26 Archibald SM, Migdisov AA, Williams-Jones AE (2002) An experimental study of the stability of copper chloride complexes in water vapor at elevated temperatures and pressures. Geochim Cosmochim Acta 66 1611-1619... 

Complex Equilibria. If one dilutes green-colored copper chloride solution with water, it turns light blue. If, however, concentrated hydrochloric acid is added, the green color is regenerated (see E9.9) - a chemical equilibrium exists ... 

Next, consider the suggestion that copper corrodes in the concentrated HC1 because of the formation of a soluble chloride complex with an equilibrium constant for the reaction Cu2+ + 4CL = (CuCl4)2- of K = 10+6. If a CuC1 2- = KL4, and the activity of the CL is that given above in the concentrated acid (acr = 5), calculate Ecell and determine whether corrosion will occur due to the formation of the complex ion. Cell reaction ... 

RAM] Ramette, R. W., Copper(ll) complexes with chloride ion, Inorg. Chem., 25, (1986), 2481-2482. Cited on page 413. 

Salts of the same complex with large organic amines have been made in methanol media by reacting copper nitrate or chloride with the respective amine and sodium azide. For example, to make the methylaniline salt 4.1 g copper nitrate in 30 ml hot methanol is added to 2 g methylaniline in 30 methanol. The blue solution is heated to near boiling, and 4.4 g sodium azide in 10 ml water is added. The red-brown solution is filtered hot to separate brown crystals. Cooling below 40 C is avoided as otherwise sodium nitrate would precipitate. The compound decomposes in water for other properties see Table XII [195]. Other copper azido complexes with organic bases are prepared like the respective metal salts, also as shown in Table XII. 

Copper ethylene chemistry is well developed, but reports of polymerizations based upon copper are rare. The amidinate ligand, A/,A/ -ditrimethylsilyl-benzamidinato, has been reported to support copper-catalyzed ethylene polymerizations. It is prepared from hexamethyldisilazane, benzonitrile, and tri-methylsilyl chloride. The resulting copper chloride complex, 2, when activated with methyl-aluminoxane, produced polyethylene with Mv = 820 000 and = 138 In another patent. 

Mechanistic studies have been carried out for neutral and cationic Cu systems [12,13b]. The proposed mechanism for [Cu(Cl)(NHC)j complexes involves the formation of [Cu(0 Bu)(NHC)] by reaction of the chloride complex with the base (Scheme 8.3). [Cu(H)(NHC)j would be formed in situ by o-bond metathesis between the terf-butoxide copper complex and the hydrosilane. The hydride copper complex is highly unstable (observable by NMR) however, it is the active species. Hence, by addition of the hydride species to the carbonyl, a second o-bond metathesis with the silane affords the expected silyl ether and regenerates the active catalyst. In the case of cationic derivatives, dissociation of one NHC occurs as the first step, which is displaced by the fert-butoxide moiety, and is the direct precursor of the active species. The hydrosilane is activated by the nucleophilic NHC, leading to the formation of the silyl ether. The activation of the silane appears to be the decisive step for this transformation. 

The process of choice for acetaldehyde production is ethylene oxidation according to the so-called Wacker-Hoechst process [route (c) in Topic 5.3.2]. The reaction proceeds by homogeneous catalysis in an aqueous solution of HQ in the presence of palladium and copper chloride complexes. The oxidation of ethylene occurs in a stoichiometric reaction of PdQ2 with ethylene and water that affords acetaldehyde, metallic palladium (oxidation state 0), and HQ [step (a) in Scheme 5.3.5). The elemental Pd is reoxidized in the process by Cu(II) chloride that converts in this step into Cu(I) chloride [step (b) in Scheme 5.3.5). The Cu(II) chloride is regenerated by oxidation with air to finally close the catalytic cycle [step (c) in Scheme 5.3.5). 

The copper(II) complex with polyaniline exhibits a higher catalytic capability for the dehydrogenation of cinnamyl alcohol into cinnamaldehyde [18, 20]. The cooperative catalysis of both components is achieved. Iron(lll) chloride is similarly employed instead of copper(II) chloride. The catalytic system is applicable to the decarboxylative dehydrogenation of mandelic acid to benzaldehyde. In these oxidation reactions, a complex catalyst consisting of polyaniline and metal salt forms a reversible redox cycle under molecular oxygen (Scheme 3.10). The copper salt appears to play a role as a metallic dopant, which is monitored spectroscopically. 

The use of silver fluoroborate as a catalyst or reagent often depends on the precipitation of a silver haUde. Thus the silver ion abstracts a CU from a rhodium chloride complex, ((CgH )2As)2(CO)RhCl, yielding the cationic rhodium fluoroborate [30935-54-7] hydrogenation catalyst (99). The complexing tendency of olefins for AgBF has led to the development of chemisorption methods for ethylene separation (100,101). Copper(I) fluoroborate [14708-11-3] also forms complexes with olefins hydrocarbon separations are effected by similar means (102). 

Aromatic amines form addition compounds and complexes with many inorganic substances, such as ziac chloride, copper chloride, uranium tetrachloride, or boron trifluoride. Various metals react with the amino group to form metal anilides and hydrochloric, sulfuric, or phosphoric acid salts of aniline are important intermediates in the dye industry. 

The volatile chlorides ate collected and the unreactedsohds and nonvolatile chlorides ate discarded. Titanium tetrachloride is separated from the other chlorides by double distillation (12). Vanadium oxychloride, VOCl, which has a boiling point close to TiCl, is separated by complexing with mineral oil, reducing with H2S to VOCI2, or complexing with copper. The TiCl is finally oxidized at 985°C to Ti02 and the chlorine gas is recycled (8,11) (see also... 

The tri- or tetraamine complex of copper(I), prepared by reduction of the copper(II) tetraamine complex with copper metal, is quite stable ia the absence of air. If the solution is acidified with a noncomplexiag acid, the formation of copper metal, and copper(II) ion, is immediate. If hydrochloric acid is used for the neutralization of the ammonia, the iasoluble cuprous chloride [7758-89-6], CuCl, is precipitated initially, followed by formation of the soluble ions [CuClj, [CuCl, and [CuCl as acid is iacreased ia the system. 

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