Ligand atom

Dyestuffs which form complexes with specific metal cations can serve as indicators of pM values 1 1-complexes (metal dyestuff = 1 1) are common, but l 2-complexes and 2 1-complexes also occur. The metal ion indicators, like EDTA itself, are chelating agents this implies that the dyestuff molecule possesses several ligand atoms suitably disposed for coordination with a metal atom. They can, of course, equally take up protons, which also produces a colour change metal ion indicators are therefore not only pM but also pH indicators. 

Ligand atoms that bond to the metal atom are in red. Tidentate (attaches to two sites). 

FIGURE 16.36 I1ie tear-shaped objects are representations of the six ligand atomic orbitals that are used to build the molecular orbitals of an octahedral complex in ligand field theory. They might represent s- or p-orbitals on the ligands or hybrids of the two. 

However, it is difficult to separate direct Cu-Cu interactions from Cu-Cu interactions taking place through the bridging ligand atoms. 

The molecular geometry of a complex depends on the coordination number, which is the number of ligand atoms bonded to the metal. The most common coordination number is 6, and almost all metal complexes with coordination number 6 adopt octahedral geometry. This preferred geometry can be traced to the valence shell electron pair repulsion (VSEPR) model Introduced In Chapter 9. The ligands space themselves around the metal as far apart as possible, to minimize electron-electron repulsion. 

Ahrland, S., Chatt, J. Davies, N. R. (1958). The relative affinities of ligand atoms for acceptor molecules and ions. Quarterly Reviews, 12, 265-76. 

Here, m is the number of electrons involved in the change, Rq the initial bond distance, and N the number of ligand atoms bonded to the metal. Covalent as well as electrostatic theories suggest that n 5. Note that for both A and /, the values appropriate for the initial state of bond length Rq should be employed. 

Ahrland et al. (1958) classified a number of Lewis acids as of (a) or (b) type based on the relative affinities for various ions of the ligand atoms. The sequence of stability of complexes is different for classes (a) and (b). With acceptor metal ions of class (a), the affinities of the halide ions lie in the sequence F > Cl > Br > I , whereas with class (b), the sequence is F < Cl" < Br < I . Pearson (1963, 1968) classified acids and bases as hard (class (a)), soft (class (b)) and borderline (Table 1.23). Class (a) acids prefer to link with hard bases, whereas class (b) acids prefer soft bases. Yamada and Tanaka (1975) proposed a softness parameter of metal ions, on the basis of the parameters En (electron donor constant) and H (basicity constant) given by Edwards (1954) (Table 1.24). The softness parameter a is given by a/ a - - P), where a and p are constants characteristic of metal ions. 

In the case of covalent compounds, crystal-field theory is a poor model for estimating electric field gradients because of the extensive participation of ligand atomic orbitals in the chemical bonds. MO calculations are a much better choice, since the corresponding interactions are considered, and realistic (noninteger) population numbers are obtained for the central metal as well as the ligand atomic orbitals. 

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