Metal-ligand complex, stoichiometry

This is simplified for titrations involving EDTA where the stoichiometry is always 1 1 regardless of how many electron pairs are involved in the formation of the metal-ligand complex. 

Molecular absorption, particularly in the UV/Vis range, has been used for a variety of different characterization studies, including determining the stoichiometry of metal-ligand complexes and determining equilibrium constants. Both of these examples are examined in this section. 

Mole-ratio plots used to determine the stoichiometry of a metal-ligand complexation reaction. 

Both the method of continuous variations and the mole-ratio method rely on an extrapolation of absorbance data collected under conditions in which a linear relationship exists between absorbance and the relative amounts of metal and ligand. When a metal-ligand complex is very weak, a plot of absorbance versus Ay or n-J m may be curved, making it impossible to determine the stoichiometry by extrapolation. In this case the slope ratio may be used. 

Using this data, determine the stoichiometry of the metal-ligand complex. 

The shift in the voltammogram for a metal ion in the presence of a ligand may be used to determine both the metal-ligand complex s stoichiometry and its formation constant. To derive a relationship between the relevant variables we begin with two equations the Nernst equation for the reduction of O... 

Complexation of dendritic ligands 1 and 2 with lanthanide ions (Nd3+, Eu3+, Gd3+, Tb3+, Dy3+) [17f] leads to results qualitatively similar to those obtained upon Zn2+ complexation (see above) an increase in the monomer naphthalene emission band at 337 nm and a complete disappearance of the exciplex band at 480 nm. However, the complex stoichiometry is different. Emission data were best fitted considering the formation of 1 3 and 1 2 (metal/ligand) complexes (log f 1 2 = 14.1 and log [ivi = 20.0) in the case of 1 and a 1 3 (metal/ligand) complex (log / 1 3 = 20.3) for compound 2. Therefore, at low metal ion concentration, only the [M(2)3]3+ species is present, as also demonstrated by NMR titration. It is likely that in this complex... 

The stability constant is probably the most important quantitative parameter for the characterization of a metal-ligand complex in that it provides a numerical index of the affinity of the metal cation for the ligand and allows the development of quantitative models able to predict the speciation of metal ions in the system studied. Several different theoretical and experimental approaches have been attempted for the determination of stability constants of metal—HS complexes and modeling metal-HS complexation reactions. Data analysis and interpretation is, however, still controversial, due to the intrinsically complex and ill-defined nature of HSs. The multiligand, polyelectrolitic nature of HS macromolecules results in the inability to describe quantitatively the types, concentrations, and strengths of the several nonidentical binding sites in HSs and in the impossibihty to ascertain and measure the stoichiometry of metal-HS complexation (MacCarthy and Perdue, 1991). 

Stability constant determinations were based on the methods of Shuman and Woodward (43,44) using ASV complexometric titration. The conditional formation constant for the formulation of a metal-ligand complex with an assumed stoichiometry of 1 1 can be determined from Equation 16... 

It is possible to obtain fairly reliable values for many complexes of 1 1 (metal ligand) stoichiometry by using an extended empirical equation in which the dielectric constant is dependent on the cationic charge (21). For the complexation reaction ... 

As was suggested in the preceding discussion, most of the arene complexes isolated by metal-atom techniques are benzene derivatives. However, heterocyclic ligands are also known to act as 5- or 6-electron donors in transition-metal 7r-complexes (79), and it has proved possible to isolate heterocyclic complexes via the metal-atom route. Bis(2,6-di-methylpyridine)Cr(O) was prepared by cocondensation of Cr atoms with the ligand at 77 K (79). The red-brown product was isolated in only 2% yield the stoichiometry was confirmed by mass spectrometry, and the structure determined by X-ray crystal-structure analysis, which supported a sandwich formulation. 

Otsuka et al. (107) describe [Ni(CNBu )2], as a reddish brown microcrystalline substance, which is extremely air-sensitive. It can be recrystallized from ether at —78°C, and is soluble in benzene in the latter solution the infrared spectrum (2020s, br, 1603m, 1210m) and proton NMR (three peaks of equal intensity at t8.17, 8.81, and 8.94) were obtained. Neither analytical data nor molecular weight is available on this complex. The metal-ligand stoichiometry is presumably established by virtue of the molar ratio of reactants and by the stoichiometries of various reaction products. 

Based on the fact that pi-acids interact with the trinuclear gold] I) pi-bases, TR(carb) and TR(bzim), the trinuclear 3,5-diphenylpyrazolate silver(I) complex was reacted with each. Mixing [Au3(carb)3] or [Au3(bzim)3] with [Ag3(p,-3,5-Ph2pz)3] in CH2CI2 in stoichiometric ratios of 1 2 and 2 1 produced the mixed metal/mixed ligand complexes in the same gold-silver ratios. The crystalline products were not the expected acid-base adducts. It is suspected that the lability of the M-N bond (M=Au, Ag) in these complexes results in the subsequent cleavage of the cyclic complexes to produce the products statistically expected from the stoichiometry of materials used [74]. As a result of the lability of Au-N and Ag-N bonds, and the stability of... 

The data of Loukidou et al. (2004) for the equilibrium biosorption of chromium (VI) by Aeromonas caviae particles were well described by the Langmuir and Freundlich isotherms. Sorption rates estimated from pseudo second-order kinetics were in satisfactory agreement with experimental data. The results of XAFS study on the sorption of Cd by B. subtilis were generally in accord with existing surface complexation models (Boyanov et al. 2003). Intrinsic metal sorption constants were obtained by correcting the apparent sorption constants by the Boltzmann factor. A 1 2 metal-ligand stoichiometry provides the best fit to the experimental data with log K values of 6.0 0.2 for Sr(II) and 6.2 0.2 for Ba(II). 

Similarly, the apparent stoichiometry of a crown complex in the solid is not necessarily a reliable measure of the actual metal-ligand binding situation. The complex of rubidium thiocyanate with dibenzo-18-crown-6 has an apparent metakligand ratio of 2 3 in the solid. However, the X-ray structure reveals that, in fact, the complex crystallizes such that one in three of the crown molecules in the lattice do not contain a Rb+ ion. Thus the true stoichiometry of the complex of this crown with RbSCN is 1 1. 

Copper(II)-aminoglycoside complexes are often isolated as monomeric species over a wide pH range. The coordination complex is usually formed in 1 1 metal ligand stoichiometry, and 1 2 metal ligand stoichiometric complexes are rare. ... 

The guest cations hitherto examined cover broadly uni- to trivalent and inorganic to organic ions that include alkali, alkaline earth, heavy and transition metal ions, as well as (ar)alkyl ammonium and diazonium ions. As to the complex stoichiometry between cation and ligand, both 1 1 stoichiometric and 1 2 sandwich complexes are analyzed. The solvent systems employed also vary widely from protic and aprotic homogeneous phase to binary-phase solvent extraction. 

Aromatic polyalcohols act as strong coordinating agents and Table 17 summarizes reported formation constants. The complexes are quite stable this behaviour has been used for the qualitative and quantitative determination of vanadium (e.g. refs. 494 and 495). At pH 3-4, an initial vanadyl catechol complex slowly converts to a tris complex.496 In fact complexes with 1 3 metal-ligand stoichiometry have been isolated (see below), but since in the equilibrium (30) no protons are consumed or liberated, [VO(cat)2]2- and [V(cat)3]2 are not distinguishable by potentiometric studies. 

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