2P32 – Principles of Inorganic Chemistry Dr. M.

Pilkington

Lecture 12 –Octahedral Substitution Reactions

The most extensively studied reactions of coordination compounds

 Measuring rates of water exchange in aquo metal ions

 Mechanisms of substitution reactions: dissociative vs

associative activation.

 Evidence for the dissociative mechanism for octahedral

complexes

 Factors affecting the rate of octahedral substitution.

Rate constants for water exchange for various ions

[M(H2O)n]x+ + 18OH [M(H2O)n-118(OH2)]x+ + H2O
Very slow 2
Very Fast
K > 10-3 to 10-6 sec-1 K > 108 sec-1

Group 1A – as we go down the group the cations are getting larger and the charge
density decreases so the Mn+-OH2 bond is getting weaker and more easily broken
Group 2A – the charge density is larger (doubly charged) so the strength of the
bond is greater so the rate of exchange is slower

1
 Classes 2 and 3 - Includes most of the first row TM ions and the

lanthanides plus Be2+, Al3+, V2+. Rate constants 1 to 108 sec-1.

 These elements who tend to undergo water exchange and ligand exchange

reactions.

 For T.M. metal ions the correlation of rate with size is not obeyed, e.g. Cr2+, Ni2+,

and Cu2+ have identical radii.

 Mn2+ > Fe2+ > Co2+ substitution rates decrease across the series. This is

due to the increase in Zeff

ff across the series and increase in E(M--L).

 d- electron configurations are important because the CFSE will affect

the rates of exchange here.

Class 4 - Rate constants are in the range 10-3-10-6 sec-1. This includes

Cr3+, Co3+, Rh3+, Ir3+, Pt2+.

 For these metal ions the rate of exchange is partially related to the size of the

cations and p
partly
y to the CFSE.

 The basic assumption is that the significant contribution to the activation energy

in a substitution reaction is the change in d-orbital energy on going from the

ground state of the complex to the transition state.

 d3 and d6 ions are predicted to be inert e.g. Rh3+, Cr3+ and Co2+

2
  For transition metal ions the electronic configurations are important because
the CFSE will affect the rates of exchange here. For these metal ions the rate
of exchange is partially related to the size of the cations and partly to the
CFSE. (see handout).

 Remember this p
plot from lecture 10. This
shows that the highest OSPE is for low
spin d6 and d3 octahedral complexes, d4 and d7
configs also have some OSPE. d0 and d10 have
none.

 It is important to be able to rationalize what effect the CSFE has on increasing

the activation energy for the formation of a 5- or 7-coordinate intermediate.
 You need to be able to rationalize why six coordinate hexaaquo complexes of
transition metal ions with d3 or d6 configuration are kinetically inert with
respect to substitution reactions.

2. Reaction Mechanisms for Octahedral Substitution

 There are only two kinds of substitution reactions that can be studied:

i. Aquation – replacement of ligand X by H2O, where X is the labile ligand.

ML5X + H2O ML5H2O + X

ii. Anation – replacement of H2O by ligand X- (anion)

ML5H2O + X- ML5X + H2O

N.B. The direct replacement of X by Y cannot be studied:

ML5X + Y ML5Y +X is not known.

It always goes via the aquo complex, i.e. in two steps, the replacement of one
ligand with water, then water is replaced with another ligand.

3
Possible Mechanisms for:
ML5X + Y ML5Y + X (X = H2O, Y = anion or vice versa)

1. Associative (A) – via a 7-coordinate intermediate

X X Y
Y
L L
slow fast
+ Y
-X
L L
L
7 co-ordinate
intermediate
the first step is slow since the
incomingY causes steric hinderance

X Y L
L L Y
or
L M L L M
L X
L L
L
"monocapped "pentagonal
octahedron" bipyramidal"

 Rate determining step (slow step) is the collision between the original
complex ML5X and the incoming ligand Y to produce a 7 coordinate
intermediate ML5XY.

 The second faster step is dissociation of the X ligand to produce the

desired product. The associative mechanism predicts that the rate of
reaction depends on the concentration of ML5X and Y.

Rate = k1[ML5X][Y]

y the case when Y is H2O,, see later!

but note this is not strictly

4
2. Dissociative (D) – via a 5-coordinate intermediate (corresponds to
organic SN1)

X Y

-X fast
slow +Y
5 co-ordinate
intermediate

L L
L Y
or
L M L L M
L X
L
"square "trigonal
pyramidal" bipyramidal"

X Y

-X fast
slow +Y
step 1 step 2
5 co-ordinate
intermediate

 Rate determining step “bottleneck step” is the slowest reaction in a

mechanism. This rate determines the overall rate of reaction.

 The dissociative mechanism – predicts that the rate of overall

substitution reaction depends on only the concentration of the original
complex [ML5X], and is independent of the concentration of the
incoming ligand [Y].

Overall rate = rate of rate determining step (1)

= k1[ML5X]

5
 So life seems simple ….

 If we determine the rate law for the reaction if it depends on only

[ML5X] then it is dissociative.

 If
f it depends
d d on [ML5X]and
d [Y] then
h it is associative.

 BUT - coordination chemistry kinetics are not quite so simple

(unfortunately  ).

 Additional complications
 the actual mechanisms maybe
y more complicated
p than those
differentiated between A and D.
 Experimental conditions may “mask” the dependence of a rate on the
concentration of the incoming ligand.

For an Associative Mechanism – we have seen that:

 Rate determining step (slow step) is the collision between the original complex ML5X and the

incoming ligand Y to produce a 7 coordinate intermediate ML5XY.

 The second faster step is dissociation of the X ligand to produce the desired product. The

associative mechanism predicts that the rate of reaction depends on the concentration of

ML5X and Y.

Rate = k1[ML5X][Y]

but note this is not strictly the case when Y is H2O. The concentration of water is so

large that it is essentially a constant, we cannot dilute water!

Hence Rate = k1[ML5X]

and the experimental conditions “mask”

mask the dependence of a rate on the concentration of

the incoming ligand.

 Now we are unable to distinguish between the associative and dissociative mechanism from

the reaction kinetics.

6
3. The Interchange Mechanism (I)
As Y begins to bond X begins to leave. i.e. the bond making to Y and
bond breaking to X occur simultaneously (organic SN2)

X Y X Y Y

+ X-

Bond Breaking Bond Making

Although we speak generally about associative and disassociative reaction

mechanisms, the terms A and D are reserved for situations where 7 and 5
coordinate intermediates have actually been isolated and positively
identified. If no intermediates have been isolated or identified the
designations Id and Ia are more appropriate.

Experimental Conditions
There is masking of concentration dependence in aqueous solution.
 An dissociative mechanism is first order in the concentration of the
complex reactant.
 An associative mechanism is first order in both complex reactant and
the
h incoming
i i water ligand.
li d

A mechanism
For example ML5X + H2O ML5H2O

 The concentration of H2O (55M) in aqueous solution is so large it is very

nearly constant.
 So it is combined with k1 and the resulting rate law is “pseudo’
pseudo first
order.
 The dependence of the associative mechanism on the concentration of
the incoming ligand has been masked.

7
 For this reaction we cannot determine the Y dependence because
H2O exchange is more likely to occur. We cannot do anything about
this because we cannot vary the concentration of H2O.
X Y
H2O
+Y
+ H 2O

Water is in great excess over Y

H20 replacement of X proceeds more rapidly than replacement of
H2O by Y.

Conclusions
 The rate law for all of these mechanisms is identical:
 Rate = k1[ML5X]
 So we cannot use the rate law to decide between the two mechanisms.
 BUT we now know that dissociative mechanisms are generally
preferred! – How can we deduce this?

3. Additional Evidence for a Dissociative Pathway for Octahedral

Substitution Reactions

What other data can we use? - 3 types:

i. Entering Group
ii. Leaving Group
iii Steric
iii. St i HiHindrance
d

i. Entering Group Effect

[Ni(H2O)6]2+ + L [Ni(H2O)5L]2+ + H2O

We can vary L (refer to Table 5.1 in text)
If we compare the rate constants for the substitution reactions, look at their values
then we can see that the largest difference is for anionic compared to neutral
ligands:
For example: NH3 = 3x103, CH3COO- = 30 x 103 so a factor of 10 difference.

8
So the conclusion is that the rate doesn’t depend on the incoming ligand significantly
which is consistent with the loss of water being rate determining and a dissociative
rate determining step which a water molecule breaks away from the Ni(II) and in a
succeeding fast step is replaced by L.

ii. Effects of Leaving Group

Table 5.2 shows how the rate of the reaction measured by (k, s-1) now depends on the
strength of the metal-ligand bond.

The rate constants k refer to the following reactions:

k
[Co(NH3)5L]2+ +H2O [Co(NH3)5(H2O)]3+ + L-

The equilibrium constants Ka refer to the following anation reactions:

Ka
[Co(NH3)5(H2O)]3+ + L- [Co(NH3)3L]2+ + H2O

The stronger
g the M-L bond the larger
g the equilibrium
q constant Ka, the
slower the reaction (k, s-1).

9
The rate constant- such variation is consistent with a rate determining step in which M-bonds of varying
strength are broken.
For equilibrium constants for the reactions in which water is replaced by L- the only major difference would
seem to be the strength of the M-L bond.

 As the M-L bond strength increases it becomes more difficult to remove the L,
and the rate decreases.
 For the 7 ligands NCS- has the slowest rate (5.0 x 10-10 s-1), NO3- has the
fastest rate (2.7 x 10-5 s-1). i.e. NCS- forms a very strong bond and is not
replaced as fast.
 Comparing equilibrium constants for the complexes:
[Co(NH3)5(H2O)]2+ + NCS- [Co(NH3)5NCS]3+ + H2O
Ka = 470 M-1
[Co(NH3)5(H2O)]2+ + NO3- [Co(NH3)5ONO2]3+ + H2O
Ka = 0.08 M-1
We can say that NCS is very stable and the NO3 complex is not.
 The rate determining step depends on the breaking M-L bond so the weaker
bond, i.e. the nitrate is faster. This is consistent with a dissociative mechanism
where the slow step is the ligand leaving to form a 5-coordinate intermediate.

10
 To Summarize see:
Figure 5.6 = the largest equilibrium constants (Ka = stronger bonds).
We plot logKa (a measure of the M-L bond strength) versus logk (a measure of the rate of the
aquation). We obtain a straight line.
The plot shows that the stronger the M-L bond the slower the rate of aquation.

 For example:
[(H3N)CoNCS]2 + + H2O [Co(NH3)5H2O] 3+ +NCS-
100, 000 x slower than replacement by NO3-

[Co(NH3)5(ONO2)]2+ + H2O Table 5.2

 Conclusion - if we cannot get water in until the bond is broken and if the
bond is strong, then H2O cannot get in, in this case it is the group that
determines what is going on.
 This is further evidence to support a dissociative pathway for octahedral
substitution reactions.

11
 iii. Steric Hindrance
 Consider the following two reactions:
[CoCl2(en)2]+ + H2O [CoCl(H2O)(en)2]+ + Cl-

[CoCl2(Me4en)2]+ + H2O [CoCl(H2O)(Me4en)2]+ + Cl-

H2N NH2 H2N NH2

en Me4en

We can compare the rates of reaction for:

Cl Cl

N N N N

N N N N

Cl Cl

reaction is 1000 times faster than reaction with

[CoCl2(en)2]+
For this dissasociative reaction – steric crowding is reduced by the loss of Cl-, if
it was associative we would go via a 7-coordinate intermediate so we would
expect the reaction to be considerably slowed by steric strain. It is not!

Study Aid: Past Exam Question (Mid Term 2007)

1. (5 marks) Transition metal complexes undergo ligand substitution reactions by
either associative (A) or dissociative (D) mechanisms. Show that you understand
these terms by drawing diagrams or writing equations to show the reaction
mechanism for each of the following reactions:
(i) [PtCl4]2-
2 + NH
3 [PtCl3(NH3)]- + Cl- (A mechanism)
h i )
(ii) [Co(NH3)5Cl]2+ + H20 [Co(NH3)5H2O]3+ + Cl- (D mechanism)

12
4. Factors Affecting the Rate of Octahedral Substitution.

1. Size and Charge of Metal – the strongest bonds occur for the
smallest size and higher charge on the metal.

2
2. Change in CFSE – complexes with d3, low spin d6 configurations and d8
exchange ligands slowly. This is because you loose a lot of crystal
field stabilization energy when going to 5 co-ordinate. (any geometry
is less than octahedral in terms of CFSE).
Look at the handout
If we compare Al3+ and Cr3+
Both metals have the same size
Cr3+ has 3 d electrons and Al3+ has none
Cr 3+ exhibits slow exchange whereas exchange is rapid for Al3+

CFSE = 1.0o

CF E = 1.2o
CFSE 12

e.g. d0 Al3+ e.g. d3 Cr3+

13