CH307

Inorganic Kinetics
Dr. Andrea Erxleben
Room C150
[email protected]
Textbook:

Inorganic Chemistry
C. E. Housecroft and A. G. Sharpe
2nd edition: Chapter 25
3rd edition: Chapter 26

Topics

Kinetically labile and inert complexes

Dissociative, associative and interchange mechanisms

Activation parameters

Substitution in square planar complexes

Substitution and isomerization in octahedral complexes

Electron-transfer reactions

1 Ligand Substitution
[MLxX] + Y [MLxY] + X
X is the leaving group and Y is the entering group.
Metal complexes that undergo substitution reactions with t1/2
1 min. at 25 C are called kinetically labile. If t1/2 > 1 min.,
the complex is kinetically inert (H. Taube).
Examples:
Cr(III) complexes are generally inert:
[Cr(en)2(ox)]+ + 4 H2O [Cr(ox)(H2O)4]+ + 2 en
(en = ethylendiamine, ox = oxalate, practical 5)

slow

Cu(II) complexes are generally very labile:

[Cu(H2O)4]2+ + 4 NH3 [Cu(NH3)4]2+ + 4 H2O
(practical 6)

fast

There is no connection between the thermodynamic

stability of a complex and its lability towards
substitution!
Example:
[Ni(CN)4]2- is thermodynamically very stable (high complex
formation constant), but kinetically labile:
[Ni(CN)4]2- +
t1/2 = 30 s

13CN

[Ni(CN)3(13CN)]2- + CN-

1.1 Types of Substitution Mechanisms

dissociative (D)
associative (A)
interchange (I)
1. Dissociative Reaction Mechanism
intermediate

MLxX

MLx + X

MLx + Y

MLxY

two-step pathway
formation of an intermediate
coordination number of the intermediate is lower than
that in the starting complex
corresponds to SN1 mechanism for organic compounds

2. Associative Reaction Mechanism

intermediate
MLxX + Y

MLxXY

MLxXY

MLxY

+ X

Example:
[PtCl4]2- + NH3 {PtCl4(NH3)}2- [PtCl3(NH3)]- + Cl

two-step pathway

formation of an intermediate

coordination number of the intermediate is higher than

that in the starting complex

3. Interchange Reaction Mechanism

MLxX + Y

Y....MLx....X

MLxY + X

transition state

Bond formation between the metal and entering group

is concurrent with bond cleavage between the metal
and the leaving group.

corresponds to SN2 reaction in organic chemistry

no intermediate

1.2 Intermediates and Transition States

transition
state

Gibbs
energy

transition
state

intermediate
reactants

reaction profile for

dissociative and
associative reaction
mechanism

products

reaction coordinate

intermediate
occurs at a local minimum
can be detected by spectroscopy and, sometimes, isolated
transition state
occurs at an energy maximum
cannot be detected or isolated

Summary
Dissociative and associative mechanisms
involve

two-step

pathways

and

an

intermediate.
An interchange mechanism is a concerted
process where there is no intermediate.

1.3 Activation parameters

Gibbs energy of activation G
Gibbs
energy

G2
G1

Gibbs energy relationship with enthalpy and entropy:

G = H - TS
Analogously for Gibbs energy of activation:
G = H - TS

H = enthalpy of activation
S = entropy of activation

Relationship between rate constant and enthalpy

and entropy of activation
ln k
T

k
T
R
k
h

=
=
=
=
=

H
k
=
+ ln
RT
h

S
+
R

rate constant
temperature in K
molar gas constant = 8.314 J K-1 mol-1
Boltzmann constant = 1.381.10-23 J K-1
Planck constant = 6.626.10-34 J s

The enthalpy of activation and the entropy of activation

can be determined by measuring the rate constant at
different temperatures:
k
Plotting ln
T
H
slope R

1
against
T

gives a straight line with

and intercept

ln k
T

k
ln
h

S
+
R

A plot of ln k vs. 1
T
T
is called an Eyring plot.
1
T

Example: [Pt(dien)Cl]+ + H2O [Pt(dien)(H2O)]2+ + Cl20

15

[s-1]

k
6.01 x 10-6
3.19 x 10-5
1.47 x 10-4

10

slope = -10001.37

5
ln(k/T)

T
298
313
328

intercept = 15.89

0
-5
-10
-15

23.76
intercept =

-20
0.000

k
ln h

S
+
R

0.001

0.002

0.003

1/T

= 15.89

S = (15.89 - 23.76) x 8.314 = -65.43 J K-1 mol-1

H
slope = R

= -10001.37 H = 83.18 kJ mol-1

G = H - TS
at r.t: G = 83.18 298 x (-0.06543) = 102.68 kJ mol-1

Volume of Activation V
associative mechanism:
MLxX + Y {MLxX...Y} MLxXY
transition
state
The transition state is compressed relative to the reactants,
i.e. has a smaller volume. We say the volume of activation
V is negative.
dissociative mechanism:
MLxX

{MLx...X}
MLx +
transition
intermediate
state

X-

The transition state has a greater volume than the initial

state. The volume of activation V is positive.

The value of the volume of activation can be used to

distinguish between dissociative and associative
mechanisms:
A negative value of V indicates an associative
mechanism, a positive value suggests that the
mechanism is dissociative.
Typical values:
[(NH3)5M(H2O)]3+ + H2O* [(NH3)5M(H2O*)]3+ + H2O
V [cm3 mol-1]
(NH3)5Co3+

+1.2

(NH3)5Rh3+

-4.1

(NH3)5Cr3+

-5.8

The value of the volume of activation can be determined

by measuring the rate constant at different pressures.
dissociative mechanism:
volume of transition state greater than initial state
increase in pressure decrease in rate constant
associative mechanism:
volume of transition state smaller than initial state
increase in pressure increase in rate constant
Example:
[Fe(CN)5(NH2Me)]3- + py [Fe(CN)5(py)]3- + MeNH2
p / MPa
5
25
50
75
100

k / s-1
0.026
0.022
0.017
0.013
0.011

dissociative
mechanism

When an associative mechanism is

operative, the rate constant increases
with increasing pressure.
In the case of an dissociative mechanism,
the rate constant decreases with
increasing pressure.

1.4 Substitution in Square Planar Complexes

square planar complexes:

metal ions with d8 configuration (RhI, IrI, PtII, PdII, AuIII)

best studied: PtII complexes
rate of ligand substitution relatively slow
convenient to measure

Nucleophilic substitution reactions in square planar

PtII complexes usually proceed by an associative
mechanism.
Evidence: negative values for V

[ ] will be used for concentration of in rate

equations.
For the sake of clarity, square brackets around
formulae of complexes are therefore omitted
on the following slides.

PtL3X + Y PtL3Y + X
experimental rate law:

rate = -

d[PtL3X]
dt

= k1 [PtL3X] + k2 [PtL3X] [Y]

under pseudo-first order conditions (excess Y):

rate = -

d[PtL3X]
dt

kobs = k1 + k2 [Y]

[Y] = const.
= kobs [PtL3X]

Determination of k1 and k2:

kobs
slope k2
k1

[Y]

Plots for different entering groups (but the same solvent)

kobs

SCNBr-

[Y]

Origin of the two terms in the rate law:

There are two parallel ways of substitution:
direct substitution: entering group displaces leaving group
k2 [Y] term
solvolytic pathway: solvent molecule displaces leaving
group, then entering group displaces
solvent
rate determining step is solvolysis
independent on concentration of
entering group
k1 term
MX
S

MS

MY
Y

S = Solvent

[(dien)PtCl] + Y [(dien)PtY] + Clkobs

Plots for different

solvents, but the
same entering group

in hexane
in H2O or methanol

[Y]

H2O, methanol:
coordinating solvents, solvolytic pathway predominates
k2 (slope) = 0 ; kobs = k1
hexane:
non-coordinating solvent, only direct substitution
k1 (intercept) = 0; kobs = k2 [Y]

Substitution at square planar Pt(II) is stereoretentive.

L
T

Pt

Y
X

X
L

Pt

Pt
X
L

square
pyramide

trigonal
bipyramide

L
Pt

T
X

Pt
Y

Y
L

square
pyramide

+X
L

Trans-Effect
PtCl42- + 2 NH3

H3N

Cl
Pt

cis isomer

H3N

Cl

H3N

Cl

Pt(NH3)42+ + 2 Cl-

trans isomer

Pt
Cl

NH3

The trans-effect is the ability of ligands to direct transsubstitution.

The choice of leaving group in a square planar complex is
determined by the ligand trans to it.
Order of trans-effect: H2O, OH- < NH3, pyridine < Cl- < Br- < I< NO2- < R- < PR3 CO, CN-

Examples:
Cl

Cl

Pt
OC

NH3
Pt

OC

2-

Cl

+ 2 pyridine

Pt
I

+ NH3

Cl

Cl

py
Pt

py

1.5 Substitution and Isomerization in

Octahedral Complexes
Examples: Cr(III), Co(III)
Volumes of activation for water exchange reactions:
metal ion
V2+
Mn2+
Fe2+
Co2+
Ni2+
Ti3+
V3+
Cr3+
Fe3+

V [cm3 mol-1]
-4.1
associative
-5.4
+3.7
dissociative
+6.1
+7.2
-12.1
-8.9
associative
-9.6
-5.4

Substitution rates for aqua ligands in M(H2O)6n+

Examples:
Ni(H2O)62+ + Y Ni(H2O)5Y2+ + H2O
entering ligand
NH3
pyridine
acetate
FSCN-

k [s-1]
3 x 10-4
3 x 10-4
3 x 10-4
0.8 x 10-4
0.6 x 10-4

Co(NH3)5X2+ + H2O

Little variation in k
consistent with a
dissociative mechanism

Co(NH3)5(H2O)2+ + X

When a dissociative mechanism is operative, the rate of ligand

substitution depends on the nature of the leaving ligand.
rate: OH- < NH3 ~ NCS- < CH3COO- < Cl- < Br- < I- < NO3The stronger the M-X bond, the slower the rate. The rate
determining step involves bond breaking!

The Eigen-Wilkins Mechanism

ML6 + Y ML5Y + L
For substitution reactions of octahedral metal complexes the
following is very often observed:
At high concentration of Y, the rate is independent of [Y],
suggesting a dissociative mechanism. At low concentrations
of Y, the rate depends on [Y] and [ML6], suggesting an
associative mechanism.
These contradictions can be explained by the Eigen-Wilkins
mechanism:
Metal complex and entering ligand form an encounter
complex in a pre-equilibrium step. This is followed by loss of
the leaving ligand in the rate-determining step.

The Eigen-Wilkins mechanism:

1. Pre-equilibrium step:
ML6

KE = equilibrium
constant

KE

{ML6,Y}
weakly bound
encounter complex

2. Rate-determining step:
{ML6,Y}

ML5Y + L

k = rate constant

Formation of {ML6,Y} and back reaction to ML6 and Y are

much faster than conversion to ML5Y.
The concentration of {ML6,Y} cannot be measured directly
and usually the equilibrium constant KE can only be
estimated using theoretical models.

KE =

[{ML6,Y}]
[ML6] [Y]

[ML6] + [{ML6,Y}] = [M]total

[M]total = [ML6] + KE [ML6] [Y] = [ML6] (1 + KE [Y])
[ML6] =

[M]total
1 + KE [Y]

rate = k [{ML6,Y}] = k ([M]total [ML6])

rate = k [M]total -

[M]total
1 + KE[Y]

k KE [M]total [Y]
1 + KE [Y]

rate =

k KE [M]total [Y]
1 + KE [Y]

At low concentrations of Y, KE[Y] 1 can be assumed and

the equation simplifies to
rate = k KE [M]total [Y] = kobs [M]total [Y]

kobs = k KE

kobs can be measured experimentally.

measured experimentally
k=

kobs
KE

estimated theoretically

At high concentration of Y (e.g. Y is solvent), KE [Y] 1

can be assumed and the equation simplifies to
rate = k [M]total

Base-catalysed Hydrolysis
Substitution reactions of CoIII ammine complexes are
catalysed by OH-.
Co(NH3)5X2+ + OH- Co(NH3)5OH2+ + XExperimentally determined rate law:
rate = kobs [Co(NH3)5X2+] [OH]
Reaction mechanism:
Conjugate-base mechanism (Dcb or SN1cb mechanism)
K
2+
(1) Co(NH3)5X
+ OH
Co(NH3)4(NH2)X+ + H2O
(2) Co(NH3)4(NH2

)X+

(3) Co(NH3)4(NH2

)2+

k
+ H 2O

Co(NH3)4(NH2)2+ + Xfast

Co(NH3)5(OH)2+

NH3
NH3

5-coordinate
intermediate

H2N

Co
NH3
NH3

rate =

K k [Co(NH3)5X2+] [OH]
1 + K [OH]

if K [OH] 1, then
rate = K k [Co(NH3)5X2+] [OH]
= kobs [Co(NH3)5X2+] [OH], where kobs = K k

Cis-trans Isomerization in Octahedral Complexes

trans-MX4Y2 trans-MX4Y2 + cis-MX4Y2
mechanism:
(1) Formation of a 5-coordinate intermediate:
MX4Y2 MX4Y + Y
(2) Berry pseudo-rotation

(3) Re-formation of the M-Y bond leads to mixture of cis

and trans isomer

2 Electron-transfer Processes
Fe(CN)63- + Co(CN)53- Fe(CN)64- + Co(CN)52-

ox. state
of M:

+3

+2

+2

+3

Two classes of electron-transfer reactions:

outer-sphere mechanism
inner-sphere mechanism

2.1 Inner-sphere mechanism

In an inner-sphere mechanism, electron transfer occurs
via a covalently bound bridging ligand.

Example:
CoIII(NH3)5Cl2+ + CrII(H2O)62+ CoII(NH3)52+ + CrIII(H2O)5Cl2+
Mechanism:
step 1: bridge formation
(NH3)5CoIIICl2+ + CrII(H2O)62+ (NH3)5CoIII(-Cl)CrII(H2O)54+ + H2O
step 2: electron transfer via bridging ligand
(NH3)5CoIII(-Cl)CrII(H2O)54+ (NH3)5CoII(-Cl)CrIII(H2O)54+
step 3: bridge cleavage
(NH3)5CoII(-Cl)CrIII(H2O)54+ CoII(NH3)52+ + CrIII(H2O)5Cl2+
CoII(NH3)52+ decomposes in water to give CoII(H2O)62+ and NH4+

evidence for this mechanism:

*Cl
CoIII(NH3)5Cl2+ + CrII(H2O)62+ CoII(NH3)52+ + CrIII(H2O)5Cl2+
*Cl = radioactive Cl
If the reaction is carried out in the presence of free *Cl,
labelled Cl is not incorporated into the product complex.
The transferred Cl must have been bound to both
metal centres during the reaction.
Common bridging ligands in inner-sphere mechanisms:

halides
OHCNNCS-

CoIII(NH3)5Cl2+ + CrII(H2O)62+ CoII(NH3)52+ + CrIII(H2O)5Cl2+

The bridging ligand is transferred from Co to Cr.
Transfer of the bridging ligand is often but not always
observed.
(NH3)5CoII Cl CrIII(H2O)54+
bond cleavage
CoII more labile than CrIII
FeIII(*CN)63- + CoII(CN)53- FeII(*CN)64- + CoIII(CN)52(CN)5FeII CN CoIII(CN)56bond cleavage

The bridging ligand is

not transferred.

Kinetics:

Most inner-sphere processes exhibit second order

kinetics.
Any of the three steps (bridge formation, electron
transfer, bridge cleavage) can be rate-determining.
Typical rate constants:
CoIII(NH3)5X2+ + CrII(H2O)62+
Bridging ligand X
FClBrN 3OHH 2O

k / M-1 s-1
2.5 x 105
6.0 x 105
1.4 x 106
3.0 x 106
1.5 x 106
0.1

2.2 Outer-sphere mechanism

Example:
FeII(CN)64- + FeIII(phen)33+ FeIII(CN)63- + FeII(phen)32+
In an outer-sphere mechanism, electron transfer occurs
without a covalent linkage being formed between the
reactants.

MIIIL6 + MIIY6 MIIL6 + MIIIY6

1. formation of a precursor complex (reductant-oxidant pair;
also called encounter complex)
MIIIL6 + MIIY6 (L5MIIIL)(YMIIY5)
2. electron transfer
(L5MIIIL)(YMIIY5) (L5MIIL)(YMIIIY5)
3. product formation
(L5MIIL)(YMIIIY5) MIIL6 + MIIIY6

Self-exchange Reactions
In a self-exchange reaction, the left- and right-hand sides of the
equation are identical. Only electron transfer, and no net chemical
reaction, takes place.
Example:
Fe(bpy)32+ + Fe(bpy)33+ Fe(bpy)33+ + Fe(bpy)32+
Gibbs energy Go ~ 0, but activation energy needed
Gibbs Energy of Activation for Outer-sphere Electrontransfer Reactions
[Fe(H2O)6]3+ + [Fe*(H2O)6]2+ [Fe(H2O)6]2+ + [Fe*(H2O)6]3+
Gibbs energy of activation G = 33 kJ mol-1

Contributions to Gibbs Energy of Activation

energy associated with bringing reductant and oxidant

together (electrostatic repulsion!)
rearrangements within the solvent spheres
energy associated with changes in bond distances
loss of translational and rotational energy on formation
of the encounter complex
energy associated with changes in bond distances
Usually, M-L bond lengths in MIII complexes are shorter than
those in corresponding MII complexes. Oxidation / reduction of
MII / MIII complex is accompanied by change in bond length!
Franck-Condon Approximation: A molecular electronic
transition is much faster than nuclear motions.
Electron transfer faster than change of bond length

Lets imagine that an electron is transferred from LxMII to LxMIII.

As electron transfer is faster than change of bond length, this
would result in excited states of LxMII and LxMIII where the MIII-L
bond lengths are longer than typical MIII-L bonds and the MII-L
bonds are shorter than typical MII-L bonds. When both
complexes return to their ground states with normal bond
lenghts, energy would be released. This would violate the first
law of thermodynamics, as a reaction with Go = 0 cannot
release energy.
Therefore the Frank-Condon restriction must apply: The
electron transfer can only take place, when M-L bond distances
in the MII and MIII are the same; i.e. the bonds in LxMIII must be
elongated and those in LxMII must be compressed before
electron transfer takes place. The energy required for
compression / elongation of bond lengths contributes to the
activation energy.
Activation energy required varies depending on
the differences in bond lengths.

Variation of activation energies rates of outer-sphere

self-exchange reactions vary considerably:
ML62+ + *ML63+ ML63+ + *ML62+
Rate constants for self-exchange reactions:
Cr(H2O)62+/3+
Fe(H2O)62+/3+
Co(H2O)62+/3+
Co(NH3)6 2+/3+
Co(en)32+/3+
Fe(phen)32+/3+
Co(phen)32+/3+
Ru(bipy)32+/3+

k [M-1 s-1], 25 C
2 x 10-5
4.2
5
8 x 10-6
7.7 x 10-5
1.3 x 107
12
4.2 x 108

Examples:
Fe(bpy)32+
Fe(bpy)33+

Fe-N = 1.97
Fe-N = 1.96

k >106 dm3 mol-1 s-1

Ru(NH3)62+
Ru(NH3)63+

Ru-N = 2.14
Ru-N = 2.10

k = 104 dm3 mol-1 s-1

Co(NH3)62+
Co(NH3)63+
k = 10-6 dm3 mol-1 s-1

Co-N = 2.11
Co-N = 1.96

Marcus-Hush Theory
Self-exchange reaction (1):
ML62+ + ML63+ ML63+ + ML62+

rate constant k11

Self-exchange reaction (2):

ML62+ + ML63+ ML63+ + ML62+ rate constant k22
Cross-reaction:
ML62+ + ML63+ ML63+ + ML62+ rate constant k12
Marcus-Hush equation

k12 = (k11k22K12f12)1/2

k = rate constants
(logK12)2
K12 = equilibrium constant
log f =
4 log(k11k22/Z2)
for cross-reaction
f~1
Z = effective collision frequency in solution

If the value of k12 calculated from the Marcus-Hush

equation agrees with the experimental value, this
provides strong evidence that the cross-reaction
proceeds by an outer-sphere mechanism.
If the Marcus-Hush equation is not fullfilled, this
indicates that another mechanism (e.g. inner-sphere
mechanism) is probably operative.

Example: Calculate the rate constant for the reaction

[Fe(CN)6]4- + [Mo(CN)8]3- [Fe(CN)6]3- + [Mo(CN)8]4from the following data:
1.) [Fe(CN)6]4-

+ [FeCN)6]3-

[Fe(CN)6]3- +

[Fe(CN)6]4-

[Mo(CN)8]4- +

[Mo(CN)8]3-

k11 = 7.4 x 102 M-1 s-1

2.) [Mo(CN)8]3-

+ [MoCN)8]4-

k22 = 2.5 x 104 M-1 s-1

3.) equilibrium constant: K12 = 1.0 x 102
4.) f12 = 0.85
Answer:
k12 = (k11k22K12f12)1/2 = (7.4 x 102 x 2.5 x 104 x 1.0 x 102 x 0.85)1/2
= 4 x 104 M-1 s-1

(experimentally found: 3 x 104 M-1 s-1)