FEN M.Se CHEMISTRY ~ SEMESTER 2 - INORGANIC CHEMISTRY WATER EXCHANGE REACTIONS Two types of water exchange rea water with solvent water 2) exch system, also termed ns are possible, 1) Exchange of coordinated ‘oordinated water with other ligands present in the nge of as anation reactions. Based on the rate of exchange of coordinated water, metal ions can be classified into four categories Class 1: The exchange of water is extremely fast. First order exchange rate constants are of the order of 10° s". These metal ions are characterized by low charge and large size. The complexes are bound by essentially electrostatic forces and include the complexes of alkali metals and larger alkaline earth metals. Class Il: The exchange of water is fast. First order exchange rate constants range from 10° to 10° s", Metal ions belonging to this group are the dipositive transition metals, Mg?" and tripositive lanthanides. These ions form complexes in which the bonding is somewhat stronger than those of Class I ions, but LFSEs are relatively small. Class III: The exchange of water is relatively slow compared with Classes I and Il, First order exchange rate constants range from 1 to 10* s!. Metal ions belonging to this ‘group are the tripositive transition metal ions stabilized by LFSEs and Be?’ and AL Class IV: The exchange of water is slow. These are the only inert complexes. First order exchange rate constants range from 10’! to 10° s'. These ions are comparable in size to Class HT ions and exhibit considerable LFSE. Eg: Cr”, Ru’*, Pe”, Mechanism Consider the replacement of water by igand L under neutral conditions. M-OH; +L —M-L+H;0 If the reaction proceeds by a dissociative mechanism, the first step is breaking the metal- water bond followed by formation of the M-L bond. M-OH; + M+H,0. M+L—> ML Let k; and k, be the rate constants for the forward and backward reactions of the first step and k be the rate constant of second step. The rate law obtained from these reactions shows a dependence on (L], even though it is derived for a dissociative mechanism. Rate = -d[M-OH|/dt 22M.Se CHEMISTRY ~ SEMESTER 2- INORGANIC CHEMISTRY = kiko[M-OH)[L (ki [H20] + kafL]) At high concentrations of L, ko{L.] > k.i[H20] ‘Then rate = Koss(M-OH3] At low concentrations of L., both L and H:0 compete for M and the rate shows a dependence on [L}. For example, the reaction of SCN’ with a Co(II!) hematoporphyrin complex shows the expected dependence of the rate on [SCN’] for lower concentration of SCN If some M-L bond making takes place before the M-OH) bond is completely broken (Jy- Interchange dissociative), the process can be described in three steps. M-OF2 + L o> M.........0H2. eek M..........OH2, Do Misiisl ¥sen.OHb M........L, OH: > M-L +H,0 Let K and kobe the equilibrium constants for first and second steps. Then rate = KK[M-OHp][L(1 + K[L]) This simplifies to kos. = kKK[L] under pseudo first order conditions. The rate law remains the same if bond making becomes more important than bond breaking (Iy- Interchange associative). Thus, the mechanism cannot be distinguished with certainty. However, the most discussions center around Iy and I, mechanisms. For reactions of Co(II1) complexes like [Co(NHs)s(H20)}°° + X" — [Co(NHs)sX°"”" + HO, most evidence supports the ls mechanism for substitution. First, there is little dependence of reaction rates on the nature of the incoming ligand. If bond making is significant (1,), the opposite would be expected. The Ig mechanism is further supported by steric arguments. For Cr(II1) complexes, there is a strong dependence of reaction rates on the nature of the entering group which supported the Ia mechanism. High pressure "OQ NMR spectroscopy has been recently used to calculate volume of activation, AV? for water exchange reactions. The data obtained for solvent exchange with [M(NH3)s(H20)” complexes show a positive AV* for Co” (+1,2 em” mot), but negative values for Cr’ (-5.8 ‘em?/mor"), Rh (-4.1 em’/mol") and 11°" (-3.2 em’/mot") suggesting an ly mechanism for Co*, but la for Cr”, Rh®* and Lr" ions. 23 a‘M.Sc CHEMISTRY ~ SEMESTER 2 - INORGANIC CHEMISTRY ELECTRON TRANSFER REACTIONS Transition metals can undergo several oxidation- reduction reactions where in there isa change in oxidation state, There are formally two types of reactions of this type- * Reactions involving simple electron transfer [Fe(CN)6}* + [In(Cl)e]?* —+[Fe(CN)e]* + [Ir(Cl}* Pn ions that can be considered as atom transfer reactions that occur with electron © Rei transfer [Co(NHs)sCI]™* + [Cr(H20)6]* — [Co(H20)6]** + [Cr(H20)sC1]* Simple electron transfer reactions involving transition metal complexes in solutions are complicated by the fact that the oxidised and the reduced species are often metal ions surrounded by shields of ligands and solvating molecules. No heat change is associated with the reaction. The reactions can be between two metal ions or between single element in different oxidation states (self exchange reactions). The electron transfer can be broadly divided into two mechanistic classes called outer sphere mechanism “and inner sphere ‘mechanism, MECHANISM OUTER SPHE es an outer sphere mechanism is established when rapid For transition metal comple: electron transfer occurs between two substituent inert complexes. (A substituent inert complex is one that undergoes substitution at a rate substantially less than the rate of electron transfer.) In this mechanism, the coordination shell of the reductant and oxidant stays intact. i.e the bonds are neither broken nor made. The electron effectively hops from one species to the other (also called tunnelling) and the ligands act as electron conduction media. An outer sphere electron transfer may be generally represented as, .-R] - formation of precursor complex O+R[0... [OveseeeeeR] [O...00...R]* > [0 followed by electron transfer and relaxation to suc R*] — chemical activation of precursor complex sor complex [O'......4.R'] + 0" +R" dissociation of separated products Here O is oxidant and R is reductant. First the oxidant and the reductant come together to form a precursor complex. Activation of the precursor complex which include reorganisation of solvent molecule and changes in metal ligand bond length occur. Final step is the dissociation of the ion pair into product 24,MISTRY /ESTER 2 - INORGANIC CHI M.Sc CHEMISTRY - ‘The salient features of electron transfer by outer sphere mechanism are, 1. Minimum electronic interactions by chemical bonding between the reactants. N The inner coordination spheres of the reactants remain unaffected | 3. The ligands in the two reactants remain as such and the bonds are neither made nor broken, 4, Rate is first order with respect to reactants. 5, Electron transfer from one stable complex to another with no breaking of M-L bond 6, Rate depends on the size of the cations present in the solution. )ol* denotes a typical example of a process shere activated complex. The The exchange of [Fe(CN)s]” and [Fe( that takes place by direct electron transfer through an outer sp rate of exchange can be studied by isotopic labelling of Fe. [Fe(CN)e* + (Fe(CN)o]™ = [Fe(CN)f* + [Fe(CNIS Feo Fe-C bond longer —_Fe-C bond shorter orbital of Fe” to tay orbital of Fe”. The bond orbitals are not equivalent. The probability of which states that there can be no jectronic transition the The electron is transferred from a t lengths are unequal. ie the energies of these the reaction can be given by Franck Condon principle appreciable change of atomic rearrangement during the time of el energies of the participating electronic orbitals must be same. Hence the ion- ligand bond Jength adjusts to intermediate value and then electron transfer takes place. Thus the actual occurs with shortening of the bonds in Fe” and lengthening of bonds in Boe process Vibrational stretching and complexes until participating orbitals are of same energy ‘low this, In specific eases, there may be angular distortion ‘accommodate the precursor structural compression along M-L bonds al of the ligand as well as solvent reorganisation to changes. Jhing motion resemble a harmonic vibration and so We assume that metal ligand stretel the potential energy curve drawn as parabolas can be approximated as @ harmonic potential vo curves. However then well, The activated complex is located at the intersection of the tw ‘molecular potential energy curves of states of same the noncrossing rule states that, per and lower curve as shown. symmetry does not cross but instead split into an up 25SEMESTER 2- INORGANIC CHEMISTRY Ms CHE : 4 TIAG® FeGFeiy “FedipFeay Potential energy diagram for a homonuclear electron transfer reaction. The activated complex is situated at I and AE is the activation energy (Gibb’s energy of activation). A general potential energy diagram for a heteronuclear electron transfer reaction can be drawn i as, : Correlation of rates with structure and electronic configuration In outer sphere mechanism, the bond distortion magnitudes have an important role in the rates of the reaction. The rate seems to be relatively great for two ions of similar geometry so that little rearrangements are needed to symmetrise the transition state enhancing a strong coupling interaction. i.e low AG;*, This will generally be the case for complexes differing by one electron in low energy tag orbitals used in ligand bonding Eg: [Mn(CN)«}*/[Mn(CN)o}* 26‘MSc CHEMISTRY ~ SEMESTER 2 - INORGANIC CHEMISTRY @. [Fe(phen);*/[Fe(phen)s}** The rates will be greatest ifthe ligands are unsaturated and pi bonding. This stabilises the lower valency state more than the higher and hence the geometries will be nearly equal. Thus [Fe(CN),}"/{Fe(CN)s}* is faster than [Fe(H0)«}*/[Fe(#20)s} If the geometry of the two ions is very different, the coupling interaction is very ‘weak since large bond distortion is needed. This is the case for fons where the electrons to be transferred occupies one of the eg orbitals used to hold a ligand, Co(ll)/Co(ll), Cra/Cram) Qs: Why the electron transfer reaction of [Fe(CN)¢]"/[Fe(CN)c]* is faster than [Co(NHs)6}*"/[Co(NHs)6}** MARCUS THEORY Marcus gave a quantitative relation for the calculation of rate constant for electron transfer by outer sphere mechanism. er = vikee"™°¥"T where ka is rate for electron transfer and AG?, the Gibb's energy of activation, given by AG* = [A (1 + 4,G°”)"}/4 where A,G" is standard reaction Gibb’s energy (obtained from the difference in standard potentials of the redox partners)~and ) the reorganization energy, the energy required to move the nuclei associated with the reacl’Mgo / the position they adopt in the product immediately before the transfer of the electron, Thiet energy depends on the changes in metal-ligand bond lengths (innersphere reorganization energy) and orientation of solvent molecules around the complex (outersphere reorganization energy), The pre exponential factor has two components, the nuclear frequency factor vy, and the electronic factor, ke. The former is the frequency at which the two complexes having already encountered each other in the solution, attain the transition state. The electronic factor gives the probability on a scale from 0 to 1 that an electron will transfer when the transition state is reached; its precise value depends on the extent of overlap of the donor and acceptor orbitals. A small reorganization energy and a value of k, close to 1 corresponds to redox couple capable of fast electron self exchange. The first requirement is achieved if the electron is removed from or added to a nonbonding orbital, as the change in metal-ligand bond length is then least, I is also likey ifthe metal is shielded from the solvent, Simple | metal fons such as aqua species typically have % well in excess of 1 eV, whereas buried redox centres in enzymes, which are well shielded from the solvent ean have values as low 2