Stability constants trends

Mohamed [63] investigated the complexation behavior of amodiaquine and primaquine with Cu(II) by a polarographic method. The reduction process at dropping mercury electrode in aqueous medium is reversible and diffusion controlled, giving well-defined peaks. The cathodic shift in the peak potential (Ep) with increasing ligand concentrations and the trend of the plot of EVl versus log Cx indicate complex formation, probably more than one complex species. The composition and stability constants of the simple complexes formed were determined. The logarithmic stability constants are log Bi = 3.56 log B2 = 3.38, and log B3 = 3.32 [Cu(II)-primaquine at 25 °C]. 

Another factor that affects trends in the stability constants of complexes formed by a series of metal ions is the crystal field stabilization energy. As was shown in Chapter 17, the aqua complexes for +2 ions of first-row transition metals reflect this effect by giving higher heats of hydration than would be expected on the basis of sizes and charges of the ions. Crystal field stabilization, as discussed in Section 17.4, would also lead to increased stability for complexes containing ligands other than water. It is a pervasive factor in the stability of many types of complexes. Because ligands that form tt bonds... 

Calorimetric studies indicate that the enthalpies of complexation tend to show related trends to the observed stability constants and display selectivity peaks, although there is not necessarily a coincidence between the two sets of peaks. Complexation is characterized by the entropy becoming progressively less positive (less favourable) as the cation size decreases. This is illustrated in Figure 6.5 for the complexation of 2.2.1 with the alkali metals. 

Similar results were obtained for analogous complexes of the de-( er -butyl)ated macrocycle (L24)2-. The ter7-butyl substituents do not affect the regiochemistry of this particular Diels-Alder reaction, but they clearly increase its rate. The observed trend is indicative of a small stabilization of the transition-state by hydrophobic effects (AAG 3 kJ/mol k coinpiex/k l) lckgr(nin(i = expiAAG /RT)). This would be consistent with our earlier observation that complexes bearing less polar carboxylate anions have the higher stability constants (see Section III.E). 

On the basis of the trend illustrated in Fig. 2, it is evident that the measured value of 21 for any aqueous Cu(II/I) system can be used to estimate the stability constant of the Cu L complex within about 2 orders of magnitude. This is a useful tool since only a limited number of Cu L stability constants have been determined in aqueous solution, whereas a large array... 

Because of the small concentration of the 2 1 complex the last term can be ignored. From the extreme rate values in the absence of zinc and with an excess of zinc, 2i and 22 are determined as 2.4 X 104 min.-1 and 1.57 min.-1 respectively. These values can be combined with the trend in the rate constants to give the stability constant of the reactive complex, presumably Zn(OR)(OAc), as 3 X 107. For the simple zinc complex in water the literature values of the stability constant for the 1 1 complex vary from 2.5 X 108 to 6.3 X 108. The diazo coupling reaction of the complex indicates the smaller effect of coordination vis a vis protonation since this reaction is very sensitive to such effects and does not proceed with phenols. Unfortunately the choice of cations for such a reaction is restricted since the cation should not interfere with the analytical methods used to obtain the kinetic data nor should it introduce additional reactions such as occur with transition metal cations which can catalyze the decomposition of the diazonium salt via a redox process. 

In general, the formation constants of metals with a specific ligand follow the predicted trend and increase in step with increasing metal hardness. Mg, Al, and Mn complexes, however, do not follow this trend. The stability constants of Mg and Al are well established and thus, their anomalous behaviour may indicate the limitation of this simple correlation when comparing A metals (Mg, Al) with d-transition elements (Fe). The data for Mn need to be thoroughly reviewed before any conclusions can be drawn. 

Copper(I) and silver(I) complexes are exceptions of the general trend in stability constants with electron-donating or attracting substituents. Thus most known 7i-complexes of silver and copper are less stable than their respective ethylene complexes (154 156). The steric hindrance introduced by the substituents seems to have a major effect in those systems. 

The stability constants in melts of NH4N03- H20 of ZnX+, ZnX2 (n = 1-3 X = Cl or Br), CdX+, CdX2 (n = 1.5-3 X = Cl or Br) and HgX HgX2 (n = 2.5 X = Cl or Br) have been determined.950,931 The behaviour of zinc is peculiar if the Ki and K2 values are compared with those of cadmium and mercury. The stability constants increase with temperature and the bromide is more stable than the chloride, trends which are opposite to those normally observed for the halide complexes of most metals in anhydrous or aqueous melts. The data also show... 

The stability constants show the same trend as with acetate having an extended region (Eu—Ho) of the gadolinium break. 

Complexes with IMDA and related ligands.—A series of three substituted aminoacetic acids, IMDA, HIMDA and NTA constitute another set of very interesting ligands. The stability constants of the iminodiacetic acid (IMDA) [ 465], N-hydroxyethyliminodiacetic acid (HIMDA) 466 and nitrilotriacetic acid (NTA) complexes are compared in Table 34. Based on log k values the following trend of stability is noted. The... 

This section concentrates on physical and chemical properties, and deals mainly with aquo complexes. The intention is to focus on trends, particularly in relation to the Periodic Table, which will not be apparent in later volumes with their metal-oriented arrangement. Trends in stability constants and in kinetic properties, both substitution and redox, of aquo ions are covered in Chapters 7 and 9 in Volume 1. 

Formally, complexation stability constants in water (log K) and extraction constants (logA j.J can be related via partitioning coefficients of the free ligand and its complex between the aqueous and organic phases.16 However, the latter are rarely available, and therefore the relationships between log/f and log Ktx are not widely used. Nevertheless, in many cases, the binding ability of ligands to metal in complexation and extraction processes follows the same trend. In this respect, information... 

The conditional stability constants found for the different marine areas are not very different. A trend can be observed of K increasing towards the open ocean. Thus relative stronger complexes are formed in the open ocean than in estuarine and coastal waters. Comparable values have been observed by other authors, using the same technique. Application of different techniques however, can result in several orders of magnitude higher K (Kramer, 1986). This cannot only be attributed to geographical differences. Another factor is, that different techniques have different sensitivities for the various species of the element concerned. 

Calix[4]pyrroles offer an alternative receptor site for the recognition of anions. Miyaji et al. [400] prepared a series of calixpyrrole-anthracene receptors that possess conjugated (73) and unconjugated bond pathways of different lengths (74 and 75). The stability constants (103—105 M-1 determined by NMR titration) for the anion complexes of each member of the series follows the trend... 

A tetra-cobaltocenium receptor 4 has been synthesised that is supported by a porphyrin skeleton [9]. This exhibits parallel photo- and electrochemical sensing of anions with a trend in selectivity of Cl >Br NOg. Proton NMR titrations in CD3CN showed chloride and bromide to be bound in 1 1 stoichiometry with stability constants of 860 and 820 M"1, respectively, whereas nitrate exhibited weaker binding with K=190 M"1. In the UV-vis spectrum of 4 in acetonitrile solution the Soret band (Amax=425 nm) of the porphyrin was signif-... 

Other groups have subsequently reported anion receptors that work on the same principle. For instance, an Eu(III) complex of the bis-bipyridinephen-ylphosphine oxide ligand 86 made by Ziessel and co-workers is able to sense anions by luminescence enhancement in acetonitrile, with stability constants which follow the trend fluoride>acetate>chloride>nitrate [61]. Tsukube and co-workers have investigated the properties of the Eu(III) and Tb(III) complexes of the chiral ligand 87 [62]. Anion binding was assessed by profiling luminescence enhancement in acetonitrile, and it was found that the different metal centres provided different selectivities. The emission at 548 nm of the Tb(III) complex was increased by 5.5 times in the presence of 3 equivalents of chloride compared to 2.2 for nitrate and 1.1 for acetate. Conversely the emission at 618 nm of the Eu(III) complex was increased 8.3 times by 3 equivalents of nitrate, 2.5 times for chloride and 1.0 times for acetate. Stability constants were not reported. 

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