Coordination Chemistry: Reactions, Kinetics and
Mechanisms
Introduction
• Organic Reactions are fairly well understood in terms of their mechanism.
• All we have to deal with is the chemistry of C, H, N, O, P, S.
• Inorganic reactions – More than 100 elements. Drawing generalizations isn’t easy!
• Elements in the same group do not always follow a particular trend in terms of reaction
mechanism.
• Example: Preparation of hexaamminecobalt(III) complex involves ligand displacement
and redox chemistry whereas hexaamminerhodium (III) can be prepared from reactants
that are already in +3 state.
NH3 [O]
[CoCl4]2- [Co(NH3)6]2+ [Co(NH3)6]3+
NH3
RhCl3.H2O [Rh(NH3)6]3+
Substitution in square planar complexes
• Complexes with d8 electronic configuration usually are 4 coordinate and square planar .
PREREQUISITE for formation/ stability of square planar complexes?
• Non bulky ligands
• Strong field ligands
• Why are rate studies done?
• It is possible to learn a great deal about the reaction mechanism from the rate behaviour
of the reaction.
Pt(II) complexes are preferred for rate studies. Why?
• They are stable
• Relatively easy to synthesize
• Undergo ligand exchange at a rate slow enough for easy monitoring.
N3-
PtMeCl(PMe2Ph)2 PtMe(N3)(PMe2Ph)2 + Cl-
Nucleophilic substitution
❑Square planar complexes-
HgCl2
Multiple pathways by which a ligand can
replace another.
• Nucleophilic substitution Cl2 PtCl2(PMe2Ph)2 + MeHgCl
• Electrophilic substitution Electrophilic substitution
• Oxidative addition followed
by reductive elimination
PtMeCl3(PMe2Ph)2 PtCl2(PMe2Ph)2 + MeCl
Oxidative addition Reductive elimination
Substitution Rxn in square planar complexes
= kobs [ML3X]
4 classes of substitution reactions
• Associative (A): M-Y bond is fully formed before M-X begins to break.
• Interchange associative (Ia): M-X begins to break before M-Y bond is
fully formed, but bond making is more important than bond breaking.
• Dissociative (D): M-X is fully broken before M-Y begins to form.
• Interchange dissociative (Id): M-Y begins to form before M-X bond is
fully broken, but bond breaking is more important than bond making.
THE RATE LAW FOR NUCLEOPHILIC SUBSTITUTION OF SQUARE PLANAR COMPLEX.
Complexes in which coordination number of metal is less than 6, tend to undergo associative process.
Based on the relative importance of bond breaking and bond making .........
Substitution reaction Y X
Associative (A) Interchange Dissociative (D) Interchange
Associative (Ia) Dissociative (Id)
Bond making more Bond breaking more
important than bond important than bond
breaking making
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• In solvent that are poor ligands (CCl4, C6H6) only second-order kinetic behaviour is observed. The entering
ligand presumably enters the complex directly.
• In solvents that are good ligands (H2O, Alcohols), 1st order path also contributes to the reaction mechanism as,
it competes with the incoming ligand for association with the metal complex.
• From the previous equation, we can see that repeating the reaction at various concentrations of Y (x axis), we
can obtain both K1 ( intercept c) and K2 ( slope m). This is because a plot of Kobs vs K2[Y] will give a straight line
with K1 as intercept and K2 as slope.
• Kobserved = K1 + K2[Y]
So for all reasons mentioned, it is believed that square planar complexes
proceed by association/ Ia rather than by dissociation.
❖ First order in substrate concentration but either first order or zero order in reagent
concentration
Rate = ks [PtA2LX] + ky [PtA2LX] [Y] ks = First order rate constant for a solvent-
controlled reaction
ky = Second order rate constant for reaction
with Y
❖ In experiments containing an excess of Y
kobs = ks + Ky [Y] Fig. 1 : Rates of reaction of [Pt(py)2Cl2]
with various nucleophiles in methanol at
30 oC
• When entering ligand plays an important role in determining the rate of the reaction
(square planar complexes) it is important to learn which ligands promote the most rapid
reactions.
• Trans Effect
Trans influence refers to the impact of a ligand on the length of the bond trans to it in the ground state of a complex ;
sometimes also called thermodynamic trans effect.
