LIGAND SUBSITUTION REACTIONS OF SQUARE PLANAR COMPLEXES

Most representatives series of square planar complexes are those of platinum(II).Care ful observations on the transformation in platinum (II)complexes revealed to the early investigators , that ligand substitution in platinum(II) complexes are highly stereospecific and different geometrical isomers are obtained by changing the order in which the groups are introduced.This was explained by Werner(1893) as due to the relative tendency of a ligand in a platinum(II) complex to direct an incoming substituent to its trans position,being different for different ligands and this was named the trans effect by Chernyaev.The classical example of trans effect phenomenon is the synthesis of the trans and cis isomers of
Pt(NH3)2Cl2,formerly

known as the and forms.thus,Pt(NH3)4Cl2 on heating to 250C .10min in

dry air exclusively forms trans Pt(NH3)2 Cl2,whileK2PtCl4 on treatment with NH3 in aqueous solution buffered with NH4Cl at roo temperature ,but preferably at 0C,for a few days forms cis Pt(NH3)2Cl2.85 percent yield along with other products,but excluding trans Pt(NH3)2Cl2.The formation of the different isomers is not due to use of different reaction conditions , since conversion of cis to trans or vice versa does not take place on heating.The formation of the two isomers could be explained due to trans-effect of the Cl ligand being greater than that of NH3. The preceding sections dealt with various experimental observations relating to the trans effect in Pt(II)complexes .Several theories have been advanced in attempts to explain this phenomenon. This section will describe two theories of the trans effect that have been used most successfully, and then these will be unified in terms of the M.O theory of bonding in these systems. It should be remembered that the trans effect is defined as an influence on the rate of reaction.since reaction rates are related to differences in activation energies between reactants and activated complexes , it follows that both must be considered in the theories of th e trans effect. The polarization theory stresses the importance of the ground state contribution to the rates of the reaction, whereas the bonding theory is primarily concerned with the transition state. Some difficulty does arise because both theories deal with energies have been measured,high rates of reaction are generally found to go with low energies of activation. However,it should be borne in mind that the use of simple rate data can lead to wrong conclusions when testing theories of energetics.

The order of some common ligand with regard to their trans influence is, H->PR3>SCN- >I-- CH3-CO- CN- Br- >Cl- >NH3- >OHThis sequence is similar to the trans effect sequence, with some striking exceptions notably for CO and CN- which have high trans-effect due to their pi acid character and hence strong tendency for ML pi bonding ability of different ligands being, C2H4 CO > CN- > NO2- > SCN- >I- > Br- > Cl- > NH3 >OH- .

THE POLARIZATION THEORY

On the basis of this theory the large trans effect of L in trans PtA2LX is due to its causing a weakening of the Pt-X bond.Grinberg made this suggestion and explained his hypothesis in terms of the polarizability of L before any direct evidence had been obtained on the relative bond strengths of Pt-X. Now ,as we saw in the previous section, there is considered experimental support of this bond weakening hypothesis.

For such systems what remains for an understanding of the trans effect is to be able to account for the bond weakening of Pt-X by L ligands high in the trans effect series. The electrostatic-polarization theory offers an explanation on the basis of charge distribution, as shown in figure 5.5.Thus, the primary charge on Pt(II) induces a dipole in L, which in turn induces a dipole in he metal. The orientation of this second dipole is such as to repel negative charge in group X. hence, the attraction of X for platinum is reduced , and the Pt-X bond is strengthened and weakened. The virtue of this theory is that it explains the parallelism between the magnitude of the trans influence of L and its polarizability, e.g., H->I->Cl-. Also it predicts that the effect will be more important if the central metal itself polarizable. This agrees with the experimental observations that Pt(II) is more strongly influenced and more polarizable than either Pd(II) or Pt(IV). Since this is an electrostatic theory, it immediately arouses some objections. For example, the induced dipole on Pt(II) should depend on the net charge of L more strongly than on the induced moment. Also it will be greater if the L-Pt bond distance is small. This leads o the wrong prediction that Cl- will have a larger trans effect than I-. This objection can be removed if the effect of covalent bonding in these systems is considered. It is probable that ligand of high polarizability will also form the most covalent bonds to Pt(II). Initially the trans effect due to the L-Pt covalency was explained on the basis of the valence bond theory, but it is now better accounted for on the basis of molecular orbital theory.

THE -BONDING THEORY

This theory deals only with -bonding ligands such as C2H4, PR3 , and CO and suggest that these are high in the trans effect series because they tend to stabilize the transition state for reaction. The concept of bonding in metal complexes was first introduced by Pauling in order to account for the short Ni-c bond distance in Ni(CO)4 and also for the large stability of the cyanide complexes of transition metals as compared to non-transition metals. The existence and significance of such double bonding are now generally recognized. A schematic representation of the double bond in Pt=PR3 is shown in figure 5.6. The bond is formed by the donation of a pair of electrons from phosphorus to platinum, and the bond by the overlap of a filled d orbital of platinum and a vacant d orbital of phosphorus. It would appear that the removal of electrons from the metal by bonding should have the effect of strengthening the bonds of the other ligands in general, and the trans ligand in particular. However, evidence from the various kinds of physical properties discussed earlier shows that the Pt-X bond is weakened in almost all cases where L is a good trans activator. Except for the cases of the olefins, which do not always cause bonds weakening, this seems to be true even if L is a -bonding ligand . Thus, it appears that, even for these ligands, electron donation in the bond is more important than electron removal in the bond. Admittedly much of the evidence for bond strengths is quite indirect, and some uncertainty does exist. Therefore, whether or not the Pt-X bond strength parallels the trans effect of L, especially when L is on an unsaturated group, remains somewhat equivocal. Since it does not seem clear that bond weakening in the ground state should always be sufficient to account for the effect of good trans activators, the increased rate of reaction should result from a stabilization of the transition state for reaction.

Chatt et al and Orgel independently proposed a -bonding stabilization of the activated complex to account for the trans effect. The activated complex is assumed to have a trigonal bipyramidal structure as shown in figure .5.7. Chatt et al. emphasize that removal of charge from Pt(II) by bonding of L will enhance the additionof Y and favor a more rapid reaction. Orgel stresses the increased stability of the transition state due to bonding because the electron density on Pt(II) is reduced along the Pt-X and Pt-Y directions. Such an activated complex will lead to retention of configuration and predicts that the properties of Y and L will influence the rate of reaction in a similar way. This explanation also requires that the reaction proceed by a bimolecular displacement mechanism. APPLICATIONS 1} Making use of this trans effect phenomenon and relative strengths of Pt-L bonds, Chernyaev synthesized all the three geometrical isomers of [Pt(NH3)(py)(NH2OH)(NO2)]Cl, by changing the order of introducing he different ligands, while Helman et al synthesized the three geometrical isomers of [Pt(NH3)(py)BrCl] making use of all these principles. Also interesting are the following synthesis :-

Use of NO2- in place of C2H4 yields similar result and these indicate that the transeffect of C2H4 and of NO2- are greater than that of Cl- as shown below:-

Aresenes, AsR3, behave similarly to phosphine , PR3.

2}The well known Kurnakov(1894) and Ryabchikov (1941) tests for distinguishing the cis- and trans- isomers of the type PtA2X2 are also based on trans-effect phenomenon, with thiourea (tu) and S2O32- having trans effect much higher than that Cl- . Thus, cis-Pt(NH3)2Cl2 n treating with thiourea forms cis-Pt(NH3)2(tu)22+, which

with a slight excess of thiourea forms Pt(tu)42+ due to strong trans-effect of thiourea , which then greatly labilizes the NH3 in trans position,leading to the replacement of the two NH3 ligands trans to the two tu ligands. But trans-Pt(NH3)Cl2 with tu forms trans Pt(NH3)2(tu)22+, which is stable to excess tu, since in this isomer the NH3 ligands are mtually in trans position, being cis to the tu ligands(Kurnakov,1894). On treatment with thiosulfate cis-Pt(NH3)2Cl2 forms Pt(S2O3), having a chelated S2O32- in which both the NH3 are in trans-position to the thiosulfate and hence readily replaced by the action of a slight excess of S2O32- formingPt (S2O3)22-. But trans Pt(NH3)2Cl2 with S2O32- forms trans Pt(NH3)2(S2O3)Cl- as an unstable intermediate, in which the Cl- in trans-position to S2O32- is so strongly labilized that it is replaced by a molecule of water (the solvent) forming trans-Pt(NH3)2(H2O)(S2O3) as the prduct which separates out, being very sparingly soluble, and this is stable to moderate excess of S2O32-.

3} Based on qualitative and semi-quantative observations, the ligands commonly found in platinum(II) complexes have been arranged into an approximate increasing order of their trans directing influence, known as the rans-effect series, which is as follows :-

Later observations showed that H- also has a very strong trans-effect and so also CH3C6H5- etc., and the relative trans effect of these groups are,

The relative values indicated are the relative rates(25C) for replacement in ethanol medium of Cl- in trans-Pt(Pet3)2(L)Cl by pyridine(py) under the trans effect of ligand L.