7 CHEM2025 AH LECTURE NOTES 2013 PART 2

Substitution Reactions
Terminologies.
Labile: Substitution occurs rapidly. Inert: Substitution occurs slowly or not at all. N.B. These are Kinetic terms which are not to be confused with the Thermodynamic terms, stable and unstable! e.g. The large equilibrium constant, K, (~1025) for the following reaction indicates that [Co(NH3)6]3+ is thermodynamically unstable:

[Co(NH3)6]3+ + 6 H3O+

[Co(H2O)6]3+ + 6 NH4+

Thermodynamically Unstable

Thermodynamically Stable

Despite this, [Co(NH3)6]3+ will persist for months in acidic medium! => Kinetic Inertness (slow reactivity). By contrast, Ni2+ + 4 CN [Ni(CN)4]2 K = 1022 The high formation constant, K implies high thermodynamic stability of [Ni(CN)4]2 So we would expect [Ni(CN)4]2 to be easily formed in the reaction. However, the rate of exchange of [Ni(CN)4]2 with isotopically labeled cyanide, (14CN) in solution, is immeasurably fast (by ordinary techniques). The complex [Ni(CN)4]2 is therefore thermodynamically stable, but kinetically labile. Lability: the ability for a complex to engage in substitution reactions.

There is not necessarily any relationship between thermodynamic stability and kinetic lability!

8 Thermodynamically stable complexes have large, positive, free energies of reaction, G. Inert complexes merely have large, positive, free energies of activation, G. The inertness of a complex results from the absence of a low energy pathway for a reaction.

Under different conditions, different pathways may be available. So when considering stability, one must ask Under what conditions? e.g. w.r.t. heat, light, acid, base etc. Kinetic rates of substitution can vary from ~10-9 s-1 (Cr3+) to ~109 s-1 (Li, Na, etc). i.e. over 18 orders of magnitute! The terms labile and inert are therefore relative. Generally, complexes that react within 1 minute are considered to be labile; slower inert. For inert complexes, we can use usual techniques e.g. NMR, IR, UV-VIS spectroscopy etc. to measure rates. For labile complexes, specialized methods are usually required for measuring the faster rates. Substitution Reactions (continued)

Associative vs Dissociative pathways.

Re: Addition reactions: Decomposition reactions: WZ + Y WYZ(1) RP R + P(2)

Dissociative pathway: Decomposition reaction followed by an addition reaction. e.g. in rxn (2) above, R may react with another ligand, L: R + L RL Associative pathway: Addition reaction followed by decomposition reaction. e.g. rxn (1) followed by removal of say, W: WYZ W + YZ

Substitution in square planar complexes

Complexes with d8 electronic configurations are usually 4coordinate and have square planar geometries. These include complexes of Pt(II), Pd(II), Ni(II) [also sometimes tetrahedral, but often octahedral], Ir(I), Rh(I), Co(I) and Au(III). Pt(II) complexes are attractive for kinetic study because they are: Stable Easy to synthesize Undergo ligand exchange reactions that are slow enough to allow easy monitoring. Associative pathways are predicted for Pt(II) sq planar complexes: because in 4coordinate complexes, the coordination sphere is not congested i.e. the Pt center is not sterically hindered, so it should easily react with an incoming ligand. Extensive studies with Pt(II) complexes have shown this to be true. Experimentally, it is observed that cis & trans isomers substitute with retention of stereochemistry => activated complex could be trigonal bipyramidal (?)

.
S
H 2O

Y X

.
+X
[PtL3X] + L
[Pt(NH3)3Cl]+ + NH3

+Y

activated complex

Y = External, incoming ligand; substitutes in same position (& with same stereochemistry) where the X ligand occupied. A typical substitution reaction of a Pt(II) square planar complex is:

[PtL4] + X
e.g.
[Pt(NH3)4]2+ + X-

Where L = ligand(s) originally on Pt; X = incoming ligand; S = solvent.

(Pt has same oxidation states and C.N.'s)

10 Rate Law under pseudo first order conditions ( if [X] is large => changes in [X] are insignificant during the reaction), Rate = k1[PtL4] + k2[PtL4][X].(3) OR Rate = kobs[PtL4]....(4) where kobs is the rate constant observed experimentally and kobs = k1 + k2[X].

What does the rate law tells us about the nature of the reaction?
Non-zero values (exptl) of k1 & k2 indicate that PtL4 is reacting by 2 different pathways (because there are 2 terms in the rate law, equation 3 above).

In general, A 1st order rate law can suggest a unimolecular, dissociative reaction. A 2nd order rate law can suggest a bimolecular, associative reaction.

(However such evidence can be misleading!)

From equation 3, the k2 term (2nd order overall) suggests an associative pathway (similar to SN2 reaction in organic chemistry). The k1 term (1st order), possibly dissociative?? In fact, the k1 term is experimentally observed to be solvent dependant => also associative! Solvent molecules can compete with X for PtL4 to form PtL3S. (common phenomena). Thus the 2term rate law could be written as:

Rate =

-d[PtL4] dt

= k' [PtL4][S] + k2 [PtL4][X]..(5)

Since the solvent is present in large excess, [S] is essentially constant and therefore k' [S] = k1 (substitute this into equation 5 and youll get equation 3).

Thus we can propose a mechanism with 2 different pathways which accounts for both the k' and the k2 terms:

11
fast -L

PtL4S
S k', slow

PtL3S
X

PtL4
X k2, slow -L

PtL3X
fast

PtL4X

As mentioned before, the k1 term in equation 3 could also arise from dissociation to give a 3-coordinate complex, but from experimental observations, association is more common.

Evidence for the associative mechanism involving solvent intervention is as follows:

From the experimental observations that these reactions take place faster in more nucleophilic solvents (suggests that solvent attack plays an important role).

Dissociative reactions should be accelerated by the presence of bulky ligands on Pt. However, the opposite is observed experimentally => mechanism is associative.

12 Substitution Reactions in Square Planar Complexes (continued)

The TransEffect
Square planar complexes such as Pt(NH3)2Cl2 can exist in 2 isomeric forms :

Cl Pt Cl
cis

NH3 NH3

H 3N Pt Cl

Cl NH3
trans

The stereochemistry dramatically affects the reactivity of the 2 compounds e.g. only the

cis isomer is effective as cancer treatment drug. The 2 isomers may be synthesized as
follows:
NH3 -Cl
-

[PtCl4]2[Pt(NH3)4]2+

[Pt(NH3)Cl3][Pt(NH3)3Cl]+

NH3 -ClCl-NH3

cis[Pt(NH3)2Cl2]

Cl-NH3

trans[Pt(NH3)2Cl2]

The two different synthetic routes yield only 1 isomer in each case. The last step is shown below, where the group trans to the chloro groups are the ones being replaced:
Cl Pt Cl Cl NH3 H3N NH3 Cl Pt NH3 ClNH3

Cl Pt Cl
cis

NH3 NH3 Cl Pt H3 N Cl
trans

NH3

Ligands that strongly favour substitution trans to themselves are strong transdirectors. Relative transdirecting ability of some common ligands (determined experimentally): CO ~ CN ~ C2H4 > PR3 ~ H > CH3 > Ph ~ NO2 ~ I ~ SCN > Br > Cl > py > NH3 > OH > H2O. Thus the trans-effect of Cl is greater than that of NH3.

13 The conversions from cis to trans isomers and vice versa, are catalyzed by traces of the free ligands. This is best explained by a 2 stage mechanism:

[Pt(NH3)4]2+
NH3 Cl-

H3N Pt
NH3
stage 1

NH3 NH3

stage 2

ClNH3

Cl

Cl Pt Cl

NH3 NH3
stage 2

H3 N Pt Cl

Cl NH3

NH3 Cl
-

Cl Pt Cl
Cl-

Cl NH3
NH3

stage 1

Cl-

[PtCl4]2The theoretical explanation of the trans-effect is still being debated.

Note. The Trans effect is a kinetic phenomenon, which depends on activation energies,
the stabilities of both the ground state and the activated complex are relevant.

Q. : How would you synthesize cis[PtCl(I)(py)2] from [PtCl4]2-, I- & py ?

End of CHEM2025 AH LECTURE NOTES 2013 PART 2