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Ligand Subsitution Reactions of Square Planar Complexes

Ligand Subsitution Reactions of Square Planar Complexes

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Published by Sharon Dunne

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Published by: Sharon Dunne on Sep 16, 2012
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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

known as the β and α forms.thus,Pt(NH3)4Cl2 on heating to 250°C .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 0°C,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 π –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.

.> NH3 >OH.which have high trans-effect due to their pi acid character and hence strong tendency for ML pi bonding ability of different ligands being. with some striking exceptions notably for CO and CN. C2H4 ≈ CO > CN.>I-. 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.>OHThis sequence is similar to the trans – effect sequence.≈ CN.> SCN.>NH3.> NO2.>Cl.>I.≈CH3-≈CO.> Cl.as we saw in the previous section.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. H->PR3>SCN. there is considered experimental support of this bond weakening hypothesis. . Now .The order of some common ligand with regard to their trans influence is.≈Br.> Br.

Initially the trans effect due to the L-Pt covalency was explained on the basis of the valence bond theory. This agrees with the experimental observations that Pt(II) is more strongly influenced and more polarizable than either Pd(II) or Pt(IV). which in turn induces a dipole in he metal.g. The virtue of this theory is that it explains the parallelism between the magnitude of the trans influence of L and its polarizability. the attraction of X for platinum is reduced . Since this is an electrostatic theory. H->I->Cl-. Also it predicts that the effect will be more important if the central metal itself polarizable. and the Pt-X bond is strengthened and weakened.5.Thus. the primary charge on Pt(II) induces a dipole in L. . hence. the induced dipole on Pt(II) should depend on the net charge of L more strongly than on the induced moment. The electrostatic-polarization theory offers an explanation on the basis of charge distribution. it immediately arouses some objections. It is probable that ligand of high polarizability will also form the most covalent bonds to Pt(II). as shown in figure 5.. Also it will be greater if the L-Pt bond distance is small. The orientation of this second dipole is such as to repel negative charge in group X.will have a larger trans effect than I-. e. but it is now better accounted for on the basis of molecular orbital theory.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. This leads o the wrong prediction that Cl. This objection can be removed if the effect of covalent bonding in these systems is considered. For example.

and CO and suggest that these are high in the trans effect series because they tend to stabilize the transition state for reaction. Therefore. this seems to be true even if L is a π-bonding ligand . . which do not always cause bonds weakening. The σ bond is formed by the donation of a pair of electrons from phosphorus to platinum. Admittedly much of the evidence for bond strengths is quite indirect. The concept of π 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. remains somewhat equivocal.6. it appears that. It would appear that the removal of electrons from the metal by π bonding should have the effect of strengthening the bonds of the other ligands in general. However. The existence and significance of such double bonding are now generally recognized. and the π bond by the overlap of a filled d orbital of platinum and a vacant d orbital of phosphorus. the increased rate of reaction should result from a stabilization of the transition state for reaction. A schematic representation of the double bond in Pt=PR3 is shown in figure 5.THE π-BONDING THEORY This theory deals only with π-bonding ligands such as C2H4. and the trans ligand in particular. especially when L is on an unsaturated group. even for these ligands. Except for the cases of the olefins. 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. 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. whether or not the Pt-X bond strength parallels the trans effect of L. electron donation in the σ bond is more important than electron removal in the π bond. and some uncertainty does exist. PR3 . Thus.

having trans effect much higher than that Cl.as shown below:- Aresenes..5. The activated complex is assumed to have a trigonal bipyramidal structure as shown in figure . APPLICATIONS  1} Making use of this trans effect phenomenon and relative strengths of Pt-L bonds.and trans. Orgel stresses the increased stability of the transition state due to π bonding because the electron density on Pt(II) is reduced along the Pt-X and Pt-Y directions. while Hel’man et al synthesized the three geometrical isomers of [Pt(NH3)(py)BrCl] making use of all these principles. AsR3. Thus. with thiourea (tu) and S2O32. Also interesting are the following synthesis :- Use of NO2.isomers of the type PtA2X2 are also based on trans-effect phenomenon. which . cis-Pt(NH3)2Cl2 n treating with thiourea forms cis-Pt(NH3)2(tu)22+. Chatt et al.in place of C2H4 yields similar result and these indicate that the transeffect of C2H4 and of NO2.are greater than that of Cl. PR3. This explanation also requires that the reaction proceed by a bimolecular displacement mechanism. by changing the order of introducing he different ligands.7. 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. behave similarly to phosphine . Chernyaev synthesized all the three geometrical isomers of [Pt(NH3)(py)(NH2OH)(NO2)]Cl.Chatt et al and Orgel independently proposed a π-bonding stabilization of the activated complex to account for the trans effect. 2}The well known Kurnakov(1894) and Ryabchikov (1941) tests for distinguishing the cis. emphasize that removal of charge from Pt(II) by π bonding of L will enhance the additionof Y and favor a more rapid reaction.

. and the relative trans effect of these groups are.leading to the replacement of the two NH3 ligands trans to the two tu ligands.formingPt (S2O3)22-. which then greatly labilizes the NH3 in trans position. being cis to the tu ligands(Kurnakov. But trans-Pt(NH3)Cl2 with tu forms trans Pt(NH3)2(tu)22+. 3} Based on qualitative and semi-quantative observations. in which the Cl.in trans-Pt(Pet3)2(L)Cl by pyridine(py) under the trans effect of ligand L.1894). the ligands commonly found in platinum(II) complexes have been arranged into an approximate increasing order of their trans directing influence.etc. being very sparingly soluble. The relative values indicated are the relative rates(25°C) for replacement in ethanol medium of Cl. which is stable to excess tu.also has a very strong trans-effect and so also CH3C6H5. which is as follows :- Later observations showed that H. On treatment with thiosulfate cis-Pt(NH3)2Cl2 forms Pt(S2O3).forms trans Pt(NH3)2(S2O3)Cl. But trans Pt(NH3)2Cl2 with S2O32. having a chelated S2O32.in trans-position to S2O32.with a slight excess of thiourea forms Pt(tu)42+ due to strong trans-effect of thiourea . known as the rans-effect series.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. since in this isomer the NH3 ligands are mtually in trans position..as an unstable intermediate.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. and this is stable to moderate excess of S2O32-.

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