Square complexes, substitution reactions

Squai e-planar rhodium I) complexes, phosphorus-nitrogen donor ligands, 44 295 Square-planar substitution reactions, 34 219-221... 

Fig. 13.3 Reaction coordinate/energy profile for a square planar substitution reaction having (a) a trigonal bipyramidal activated complex and (b) a trigonal bipyramidal intermediate. [From Burdetl, 1. K. Inorg. Chem. 1977, 16, 3013-3025. Used with permission.)...

Although in the previous section the basic concepts related to substitution reactions were explained with reference to octahedral complexes, substitution reactions are also common in square planar complexes. Studies on these complexes have resulted in a great deal of knowledge of the mechanisms of these reactions, so a brief description of the topic is presented next. 

The kinetics of square planar substitution reactions are complex, as shown in Figure 17.6. The experimentally determined rate law has two terms, as shown in Equation (17.39). 

The substitution reactions (23), where the chelate ligands are cyclo-octa-1,5-diene (cod), ethylenediamine (en), or iV,iV -dimethylethylenediamine, offer two further illustrative examples of square-planar substitution reactions, where reversible solvolysis of the substrate complex has to be considered. In these cases also, the observed rate constants depend on the concentration of the leaving ligand (X=C1 ), so the more complete rate law (2) applies. 

Transition metal square-planar complexes generally contain eight d electrons and are almost always diamagnetic. This includes complexes of Pt, Pd % Au, Rh, and Ir. While such complexes can imdergo other reactions such as redox processes, we shall focus on substitution reactions. Good reviews of square-planar substitution reactions are available. The following is a summary of some of these substitution processes, wifli emphasis on those involved with polymer formation. These substitution reactions are the most widely studied of the transition metal square-planar complex reactions. 

Square planar complexes of palladium(II) and platinum(II) readily undergo ligand substitution reactions. Those of palladium have been studied less but appear to behave similarly to platinum complexes, though around five orders of magnitude faster (ascribable to the relative weakness of the bonds to palladium). 

Solvent paths and dissociate intermediates in substitution reactions of square planar complexes. R. J. Mureinik, Coord. Chem. Rev., 1978, 25,1-30 (133). 

Application of the principle of microscopic reversibility can be used to eliminate a mechanism suggested at one time for the nucleophilic substitution reactions of square-planar platinum(II) complexes. For the sake of specificity, we take PtCl - as a typical... 

As already mentioned, complexes of chromium(iii), cobalt(iii), rhodium(iii) and iridium(iii) are particularly inert, with substitution reactions often taking many hours or days under relatively forcing conditions. The majority of kinetic studies on the reactions of transition-metal complexes have been performed on complexes of these metal ions. This is for two reasons. Firstly, the rates of reactions are comparable to those in organic chemistry, and the techniques which have been developed for the investigation of such reactions are readily available and appropriate. The time scales of minutes to days are compatible with relatively slow spectroscopic techniques. The second reason is associated with the kinetic inertness of the products. If the products are non-labile, valuable stereochemical information about the course of the substitution reaction may be obtained. Much is known about the stereochemistry of ligand substitution reactions of cobalt(iii) complexes, from which certain inferences about the nature of the intermediates or transition states involved may be drawn. This is also the case for substitution reactions of square-planar complexes of platinum(ii), where study has led to the development of rules to predict the stereochemical course of reactions at this centre. 

Rate constants for the substitution reactions of square-planar dithio-phosphates and dithiocarbonate complexes of Ni(II), Pd(II), and Pt(II), with ethylenediamine and cyanide ion as nucleophiles, have been measured in methanol. The results were compared with those obtained in previous investigations, and interpreted in terms of the stabilities of 5-coordinate species that are formed prior to substitution (377). 

Let us first consider the case of a substitution reaction in a complex of a d6 ion such as Co3+ in a strong field. If the process takes place by an SN1 process, the five-bonded transition state may be presumed to have either a trigonal bipyramid or square-based pyramid structure. The orbital energies will be determined as follows ... 

The kinetics and mechanism of ligand substitution reactions of square-planar platinum(II) dimethyl sulfoxide complexes have been exhaustively studied (173), and these workers conclude that the cis and trans influences and the trans effects of Me2SO and ethylene are similar in magnitude whereas the cis effect of Me2SO is about 100 times as large as that of ethylene. The results for reaction (5), where the stability constants, Kt, are reported to be 1.5 x 108 (L = S-Me2SO) and 4.5 x 108 (L = ethylene) corroborate this analogy (213). 

Steric hindrance is well known to slow down the rates of ligand substitution reactions in square-planar metal complexes. An example for which steric hindrance controls the aquation rate is complex 9. The effect of 2-picoline on the rate of hydrolysis of CP trans to NH3 (cis to 2-picoline) is dramatic, being about 5 times as slow as the analogous CP ligand in the nonsterically hindered 3-picoline complex (Table I) (44). 

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