Reaction with Cu

Equilibrium complexation constants for Cu reactions with natural organic matter and the details of Cu speciation are bound to remain somewhat uncertain, since the composition of the complexing molecules varies from site to site. What is not in dispute is that the fraction of dissolved copper present as free aquo Cu is probably very small in any natural water. In extremely pristine waters, hydroxide and carbonate complexes may dominate, but organic complexes usually dominate in waters containing more than a few tenths of a mg/L organic carbon. 

BCA Cu2+ reaction with peptide bonds Cu+ reaction with bicinchonate 0.2-50 pg NH4+. EDTA Suitable for solutions containing detergent... 

Figure 2.17 Chloridecatalysisofthe copper deposition reaction is quantified by the increase in the exchange current density of the rate determining Cu2+/Cu+ reaction with increasing chloride concentration (source Ref. [128]).

The radionuclide Cu emits P -particles of ideally suitable energy. It is occasionally produced via the spallation process, but more commonly via the Zn(p,2p) Cu reaction with protons of energies above 50 MeV. (Mirzadeh et al. 1986 Schwarzbach et al. 1995 Stoll et al. 2002). A recently reported method of production makes use of the Zn(p,a) Cu reaction over the energy range of 12 to 21 MeV. If highly enriched target material is used, the resulting Cu is very pure (Kastleiner et al. 1999). 

Rettner C T 1992 Dynamics of the direct reaction of hydrogen atoms adsorbed on Cu(111) with hydrogen atoms incident from the gas phase Phys.Rev. Lett. 69 383... 

Rettner C T and Auerbach D J 1996 Quantum-state distributions for the HD product of the direct reaction of H(D)/Cu(111) with D(H) incident from the gas phase J. Chem. Phys. 104 2732... 

With higher alkenes, three kinds of products, namely alkenyl acetates, allylic acetates and dioxygenated products are obtained[142]. The reaction of propylene gives two propenyl acetates (119 and 120) and allyl acetate (121) by the nucleophilic substitution and allylic oxidation. The chemoselective formation of allyl acetate takes place by the gas-phase reaction with the supported Pd(II) and Cu(II) catalyst. Allyl acetate (121) is produced commercially by this method[143]. Methallyl acetate (122) and 2-methylene-1,3-diacetoxypropane (123) are obtained in good yields by the gas-phase oxidation of isobutylene with the supported Pd catalyst[144]. 

One type of o-aminobenzyl anion synthon is a mixed Cu/Zn reagent which can be prepared from o-toluidines by / i.s-trimethylsilylation on nitrogen, benzylic bromination and reaction with Zn and CuCN[l]. Reaction of these reagents with acyl halides gives 2-substituted indoles. 

The concentrations of Fe + and in a mixture can be determined following their reaction with hexacyanoruthenate (II), Ru(CN)5 , which forms a purple-blue complex with Fe + Q max = 550 nm), and a pale green complex with Cu + ( max = 396 nm)d The molar absorptivities cm ) for the metal... 

In some cases, particularly with iaactive metals, electrolytic cells are the primary method of manufacture of the fluoroborate solution. The manufacture of Sn, Pb, Cu, and Ni fluoroborates by electrolytic dissolution (87,88) is patented. A typical cell for continous production consists of a polyethylene-lined tank with tin anodes at the bottom and a mercury pool (ia a porous basket) cathode near the top (88). Pluoroboric acid is added to the cell and electrolysis is begun. As tin fluoroborate is generated, differences ia specific gravity cause the product to layer at the bottom of the cell. When the desired concentration is reached ia this layer, the heavy solution is drawn from the bottom and fresh HBP is added to the top of the cell continuously. The direct reaction of tin with HBP is slow but can be accelerated by passiag air or oxygen through the solution (89). The stannic fluoroborate is reduced by reaction with mossy tin under an iaert atmosphere. In earlier procedures, HBP reacted with hydrated stannous oxide. 

A convenient synthesis of organochlorosilanes from organosilanes is achieved by reaction with inorganic chlorides of Hg, Pt, V, Cr, Mo, Pd, Se, Bi, Fe, Sn, Cu, and even C. The last compounds, tin tetrachloride, copper(II) chloride, and, under catalytic conditions, carbon tetrachloride (117,118), are most widely used. 

Organic solutions of HOCl can be prepared in near quantitative yield (98—99%) by extraction of CU -containing aqueous solutions of HOCl with polar solvents such as ketones, nitriles, and esters (131). These organic solutions of HOCl have been used to prepare chlorohydrins (132) and are especially useful for preparation of water-insoluble chlorohydrins. Hypochlorous acid in methyl ethyl ketone has also been used to prepare Ca(OCl)2, by reaction with CaO or Ca(OH)2 (133), and hydrazine by reaction with NH3 (134). 

Peroxymonosulphuric acid (PMSA, H SO ) proved to be a promising oxidizer in reactions with chemiluminescent substances (luminol) with participation of such ions as Mn(II), Cu(II), Ni(II), Cr(IV), V(V). The literature data show the possibility of utilization PMSA in indicating reaction with ferroin ([Fe(l,10-phenanthrolyne) ] ) which is accelerated by Mn(II) compounds. 

Absorption spectra of standard solutions of Cyt c was obtained at different concentration. Maximum of absolution was observed at wavelength 410 nm. It is known haemoglobin and other haems have absolution maximum at the same wavelength. For elaboration of selective method of Cyt c determination in semm of mice its reaction with phtalocyanine of copper was investigated. Absorption maximum of Cyt c with Cu phtalocyanine in H SO was observed at wavelength 710 nm. Dependence on optical density at 710 nm against concentration of Cyt c have linear character in range 0.162-10-"-6.49-10 mol/L. 

In the reactions of 10.13a with alkali metal terr-butoxides cage expansion occurs to give the sixteen-atom cluster 10.15, in which two molecules of MO Bu (M = Na, K) are inserted into the dimeric structure. The cluster 10.13a also undergoes transmetallation reactions with coinage metals. For example, the reactions with silver(I) or copper(I) halides produces complexes in which three of the ions are replaced by Ag" or Cu" ions and a molecule of lithium halide is incorporated in the cluster. ... 

Few industrial uses have so far been found for phosphides. Ferrophosphorus is produced on a large scale as a byproduct of P4 manufacture, and its uses have been noted (p. 480). Phosphorus is also much used as an alloying element in iron and steel, and for improving the workability of Cu. Group 3 monophosphides are valuable semiconductors (p. 255) and Ca3P2 is an important ingredient in some navy sea-flares since its reaction with water releases spontaneously flammable... 

The absolute configuration of products obtained in the highly stereoselective cycloaddition reactions with inverse electron-demand catalyzed by the t-Bu-BOX-Cu(II) complex can also be accounted for by a square-planar geometry at the cop-per(II) center. A square-planar intermediate is supported by the X-ray structure of the hydrolyzed enone bound to the chiral BOX-copper(II) catalyst, shown as 29b in Scheme 4.24. 

Kaeriyama and Shimura [34] have reported the photoinitiation of polymerization of MMA and styrene by 12 metal acetylacetonate complex. These are Mn(acac)3, Mo02(acac)2, Al(acac)3, Cu(bzac)2, Mg(acac)2, Co(a-cac)2, Co(acac)3, Cr(acac)3, Zn(acac)2, Fe(acac)3, Ni(a-cac)2, and (Ti(acac)2) - TiCU. It was found that Mn(a-cac)3 and Co(acac)3 are the most efficient initiators. The intraredox reaction with production of acac radicals is proposed as a general route for the photodecomposition of these chelates. 

The NH2 groups can be diazotized and reduced in the presence of thiosulphates and different metal ions. The effect of some metal ions, namely Fe ", Sn, Cu +, and Co on the graft yield of cotton modified with aryl diazonium groups via its reaction with 2,4-dichloro-6-(p-nitroaniline)-5-triazine in the presence of alkali and followed by reduction of nitro group was studied [4]. 

The reduced Cu(I) ions are reoxidized to Cu(II) ions hy reaction with oxygen and HCl ... 

As inert as the C-25 lactone carbonyl has been during the course of this synthesis, it can serve the role of electrophile in a reaction with a nucleophile. For example, addition of benzyloxymethyl-lithium29 to a cold (-78 °C) solution of 41 in THF, followed by treatment of the intermediate hemiketal with methyl orthoformate under acidic conditions, provides intermediate 42 in 80% overall yield. Reduction of the carbon-bromine bond in 42 with concomitant -elimination of the C-9 ether oxygen is achieved with Zn-Cu couple and sodium iodide at 60 °C in DMF. Under these reaction conditions, it is conceivable that the bromine substituent in 42 is replaced by iodine, after which event reductive elimination occurs. Silylation of the newly formed tertiary hydroxyl group at C-12 with triethylsilyl perchlorate, followed by oxidative cleavage of the olefin with ozone, results in the formation of key intermediate 3 in 85 % yield from 42. 

A further factor which must also be taken into consideration from the point of view of the analytical applications of complexes and of complex-formation reactions is the rate of reaction to be analytically useful it is usually required that the reaction be rapid. An important classification of complexes is based upon the rate at which they undergo substitution reactions, and leads to the two groups of labile and inert complexes. The term labile complex is applied to those cases where nucleophilic substitution is complete within the time required for mixing the reagents. Thus, for example, when excess of aqueous ammonia is added to an aqueous solution of copper(II) sulphate, the change in colour from pale to deep blue is instantaneous the rapid replacement of water molecules by ammonia indicates that the Cu(II) ion forms kinetically labile complexes. The term inert is applied to those complexes which undergo slow substitution reactions, i.e. reactions with half-times of the order of hours or even days at room temperature. Thus the Cr(III) ion forms kinetically inert complexes, so that the replacement of water molecules coordinated to Cr(III) by other ligands is a very slow process at room temperature. 

Brief reaction of 3-aminodibenzofuran with chlorine in carbon tetrachloride at room temperature gave the 4-chloro product. After 5 min, a 1 0.4 ratio of 3-amino-4-chloro and 3-amino-1,2,4-trichloro derivatives had formed. Subsequent diazotization and reaction with Cu(I)37 Cl gave products with a labeled chlorine in the 3-position (90SC2501). 2-Methoxydibenzofuran was brominated to give the 3-bromo (33%) and a little of the 1-bromo derivative [39JA1365 84AHC(35)2],... 

In contrast, transmetalation of the lithium enolate at —40 C by treatment with one equivalent of copper cyanide generated a species 10b (M = Cu ) that reacted with acetaldehyde to selectively provide a 25 75 mixture of diastereomers 11 and 12 (R = CH3) which are separable by chromatography on alumina. Other diastereomers were not observed. Similar transmetalation of 10a (M = Li0) with excess diethylaluminum chloride, followed by reaction with acetaldehyde, produced a mixture of the same two diastereomers, but with a reversed ratio (80 20). Similar results were obtained upon aldol additions to other aldehydes (see the following table)49. 

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