Copper hydrolysis constant

There are few data for the first monomeric hydrolysis constant of copper(II). The reviews of Plyasunova et al. (1997) and Powell et al. (2007) both favoured the data of Paulson and Kester (1980) however, these data are not consistent with other low ionic strength data (Arena et al., 1976 Sylva and Davidson, 1979) that were also able to detect the formation of the dominant polynuclear species of cop-per(II). Data are also available for this stability constant at elevated temperatures from Var yash (1985). This latter data are used from 100 to 350 "C, whereas other available data are preferred at lower temperatures. When these data are assessed, it is clear that the stabihty constant derived for 25 °C and zero ionic strength is more positive than that which would be derived from the fixed ionic strength data of Paulson and Kester (1980). Due to these facts, the data of Paulson and Kester (1980) are not retained in this review. Data for the stability constant of CuOH" are listed in Table 11.54. 

There are a few documented examples of studies of ligand effects on hydrolysis reactions. Angelici et al." investigated the effect of a number of multidentate ligands on the copper(II) ion-catalysed hydrolysis of coordinated amino acid esters. The equilibrium constant for binding of the ester and the rate constant for the hydrolysis of the resulting complex both decrease in the presence of ligands. Similar conclusions have been reached by Hay and Morris, who studied the effect of ethylenediamine... 

Rate constants and the products formed in the hydrolysis of Cl Reactive Red 194 (7.76) at 50 °C and pH values in the 10-12 region were determined by high-pressure liquid chromatography. In addition to the normal hydrolysis of the two reactive systems, the imino link between the triazine and benzene nuclei was also hydrolysed [67]. The heterobifunctional copper formazan dye Cl Reactive Blue 221 and two blue anthraquinone monofunctional reactive dyes of the bromamine acid type, namely the aminochlorotriazine Blue 5 and the sulphatoethylsulphone Blue 19, were compared in terms of their sensitivity to... 

The behavior of metal ions in reversed micelles may be more interesting, since the reversed micelle provides less solvated metal ions in its core (Sunamoto and Hamada, 1978). Through kinetic studies on the hydrolysis of the p-nitrophenyl ester of norleucine in reversed micelles of Aerosol OT and CC14 which solubilize aqueous cupric nitrate, Sunamoto et al. (1978) observed the formation of naked copper(II) ion this easily formed a complex with the substrate ester (formation constant kc = 108—109). The complexed substrate was rapidly hydrolyzed by free water molecules acting as effective nucleophiles. 

Paints were prepared from polymers of different composition and composition distribution using a standard copper thiocyanate based formulation similar to that which has been described by Hails and Symonds (11). A rotating disc technique (3) was used to measure the polishing rate (which is a measure of hydrolysis rate) of polymer and paint films. Standard coated panels were attached to a disc (Figure 4) in a radial display and this disc then rotated at a constant speed (1400 rpm) in a thermostatically controlled lank (25°C) of replenished sea water. They hydrolytic stability of the films was assessed by the rate of change of film thickness as measured by a surface profiling technique (Ferranti Surfcom). 

Metal-ion catalysis has been extensively reviewed (Martell, 1968 Bender, 1971). It appears that metal ions will not affect ester hydrolysis reactions unless there is a second co-ordination site in the molecule in addition to the carbonyl group. Hence, hydrolysis of the usual types of esters is not catadysed by metal ions, but hydrolysis of amino-acid esters is subject to catalysis, presumably by polarization of the carbonyl group (KroU, 1952). Cobalt (II), copper (II), and manganese (II) ions promote hydrolysis of glycine ethyl ester at pH 7-3-7-9 and 25°, conditions under which it is otherwise quite stable (Kroll, 1952). The rate constants have maximum values when the ratio of metal ion to ester concentration is unity. Consequently, the most active species is a 1 1 complex. The rate constant increases with the ability of the metal ion to complex with 2unines. The scheme of equation (30) was postulated. The rate of hydrolysis of glycine ethyl... 

Eichhom and his co-workers have thoroughly studied the kinetics of the formation and hydrolysis of polydentate Schiff bases in the presence of various cations (9, 10, 25). The reactions are complicated by a factor not found in the absence of metal ions, i.e, the formation of metal chelate complexes stabilizes the Schiff bases thermodynamically but this factor is determined by, and varies with, the central metal ion involved. In the case of bis(2-thiophenyl)-ethylenediamine, both copper (II) and nickel(II) catalyze the hydrolytic decomposition via complex formation. The nickel (I I) is the more effective catalyst from the viewpoint of the actual rate constants. However, it requires an activation energy cf 12.5 kcal., while the corresponding reaction in the copper(II) case requires only 11.3 kcal. The values for the entropies of activation were found to be —30.0 e.u. for the nickel(II) system and — 34.7 e.u. for the copper(II) system. Studies of the rate of formation of the Schiff bases and their metal complexes (25) showed that prior coordination of one of the reactants slowed down the rate of formation of the Schiff base when the other reactant was added. Although copper (more than nickel) favored the production of the Schiff bases from the viewpoint of the thermodynamics of the overall reaction, the formation reactions were slower with copper than with nickel. The rate of hydrolysis of Schiff bases with or/Zw-aminophenols is so fast that the corresponding metal complexes cannot be isolated from solutions containing water (4). 

Wall et al. built a binuclear copper(II) complex 43 in order to see acceleration of phosphodiester cleavage (52). With the substrate (50 p.M) shown, the reaction might be considered as a model for the first step of the hydrolysis of RNA, in which the alcohol function of the side chain intramolecularly attacks the Cun-activated phosphate as a nucleophile for a ring closure reaction. Compared to an analogous mononuclear complex 44 (at 1 mM), a rate constant ca. 50 times larger for 43 (at 1 mM) was observed at 25°C and pH 7, implying that the two metal ions probably cooperate. An analogous zinc(II) complex 45 was reported only as a structural model for the active site of phospholi-... 

Table 13 Rate Constants and p K, Values for the Base Hydrolysis of some Copper(II) Complexes of Dipeptide Esters at 25 °C and I -0.01 Ma...

Hay and Nolan407 have carried out a detailed kinetic study on the hydrolysis of N-2-pyridyl-methyleneaniline (117 = L) and its copper(II) complex (118). Very substantial rate accelerations were observed in this system. Base hydrolysis of [CuL(OH2)2]2+ (118) is some 105 times faster than base hydrolysis of L at 25 °C. The rate constants for this system are summarized in Table 26. 

Table 27 Rate Constants and Formation Constants for the Copper(II)-catalyzed Hydrolysis of /3-Lactam Substrates at...

Table 3-1. Rate constants for the hydrolysis of methyl glycinate, H2NCH2C02Me, in neutral water, in dilute acid and in the presence of copper(n) salts.

Menger et al. synthesized a Ci4H29-attached copper(II) complex 3 that possessed a remarkable catalytic activity in the hydrolysis of diphenyl 4-nitrophenyl phosphate (DNP) and the nerve gas Soman (see Scheme 2) [21], When 3 was used in great excess (ca. 1.5 mM, which is more than the critical micelle concentration of 0.18 mM), the hydrolysis of DNP (0.04 mM) was more than 200 times faster than with an equivalent concentration of the nonmicellar homo-logue, the Cu2+-tetramethylethylenediamine complex 9, at 25°C and pH 6 (Scheme 4). The DNP half-life is calculated to be 17 sec with excess 1.5 mM 3 at 25°C and pH 6. The possible reasons for the rate acceleration with 3 were the enhanced electrophilicity of the micellized copper(II) ion or the acidity of the Cu2+-bound water and an intramolecular type of reaction due to the micellar formation. On the basis of the pH(6-8.3)-insensitive rates, Cu2+-OH species 3b (generated with pK3 < 6) was postulated to be an active catalytic species. In this study, the stability constants for 3 and 9 and the thermodynamic pvalue of the Cu2+-bound water for 3a —> 3b + H+ were not measured, probably because of complexity and/or instability of the metal compounds. Therefore, the question remains as to whether or not 3b is the only active species in the reaction solution. Despite the lack of a detailed reaction mechanism, 3 seems to be the best detoxifying reagent documented in the literature. 

A plot of p([Cu2 ]/[Cu7ot]) 3S a function of pH for three separate titrations fall on a single curve despite up to fivefold differences in measured dissolved copper concentration at a given pH (Figure 2). This behavior of the ratio [Cu2+]/[Cujot] is indicative of the formation of mononuclear hydrolysis species and excludes the possibility that the observed reduction in free cupric ion may have been caused by precipitation of Cu(0H)2 (solid) or the formation of polynuclear complexes. Analysis of data for p[Cu2+], pECujoj] and pH in the pH range 7.7 to 10.8 indicated the presence of two hydrolysis species (CuOH and Cu(0H)2) whose stability constants are given in Table I. Our value of the stability constant for the monohydroxo complex (106.48) falls... 

Table 14 Rate Constants for the Base Hydrolysis of EDTA Methyl Esters and their Copper(II) Complexes at 25 "C and I = 0.1 M ...

The modulation of the coordination to the transition metal has not necessarily positive implications on the reactivity. For instance, we observed [50] that the copper(II) complex (8) of tetramethyl-l,2-diaminoethane catalyzes the hydrolysis of the phosphoric acid triester PNPDPP via an electrophilic mechanism which involves the pseudointramolecular attack of deprotonated water, as illustrated in (9). The electrophilic mechanism contribution to the hydrolytic process totally disappears in micellar aggregates made of the amphiphilic complex (10). Clearly, micellization does not allow the P O group of the substrate to interact with the metal ion. This could be a result of steric constraint of the substrate when bound to the micelle and/or the formation of binuclear dihydroxy complexes, like (11), in the aggregate. So, in spite of the quite large rate accelerations observed [51] in the cleavage of PNPDPP in metallomicelles made of the amphiphilic complex (10), the second-order rate constant [allowing for the difference in pXa of the H2O molecules bound to copper(II) in micelles and monomers] is higher for (8) than for (10) (k > 250). 

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