2A:

Complex stabilities, kinetics and thermodynamics

 Complex Stabilities, Kinetics and Thermodynamics

When and why is a metal complex stable?

In aqueous solution a comparison of metal complexes and their affinity

for the H2O molecule as a competing ligand has been studied. Here
are some general observations:

For a given metal and ligand, complexes where the metal oxidation
state is +3 are more stable than +2.

Stabilities of complexes of the first row of transition metals vary in

reverse of their cationic radii (in general, more on this later)

MnII < FeII < CoII < NiII > CuII > ZnII

What factors are involved?

 Labile and non-labile complexes
The rate at which one complex inter-converts into another
is determined by the height of the activation barrier
between the two:

Labile complexes: A complex with a half life of the order

of milliseconds; e.g. [Ni(H2O)6]2+ is said to be labile

Non-labile or inert complex has half-life of the order of

minutes; e.g [Co(NH3)5(H2O)]3+
 Factors affecting lability of complexes:
1. Complexes with no stabilising CFSE or chelate
effects are very labile
2. Complexes of small metal ions are less labile
due to greater M-L bonds
3. Complexes of M(III) ions are less labile than
those of M(II) ions
4. Complexes of d3 and low spin d6 config are
non-labile  high CFSE
5. Chelate complexes of metal ions with high
CFSE (e.g. [Fe(phen)3]2+) are very stable
6. Complexes of d10 ions (zero CFSE: Zn2+, Cd2+,
Hg2+) are generally labile
 [Fe(phen)3]2+

Tris-(phenantroline)iron(II)
How stable is stable? Formation constants

Formation constant: the strength of a ligand relative to the strength of the

solvent molecules (usually H2O) as a ligand.

[Fe(OH2)6]3+(aq) + SCN-(aq) [Fe(SCN)(OH2)5]2+(aq) + H2O(l)

In dilute solutions [H2O]  constant; [Fe(SCN)(OH2)52+]

Kf
[Fe(OH2)63+][SCN-]

Step-wise formation constant: formation constant of each solvent

replacement stage.
Kf1 ; Kf2........Kfn

Overall formation constant: product of the step-wise formation constants.

βn = Kf1Kf2........Kfn
 Successive formation constants
Example

Cd2+ + NH3 ↔ [CdNH3]2+ K1 = 102.65

[CdNH3]2+ + NH3 ↔ [Cd(NH3)2]2+ K2 = 102.10

[Cd(NH3)2]2++ NH3 ↔ [Cd(NH3)3]2+ K3 = 101.44

[Cd(NH3)3]2++ NH3 ↔ [Cd(NH3)4]2+ K4 = 100.93

Overall: Cd2+ + 4 NH3 ↔ [Cd(NH3)4]2+

β4 = K1 x K2 x K3 x K4 = 10(2.65 + 2.10 + 1.44 + 0.93)

= 107.12
Trends in successive formation constants
The general trend  Kf1 > Kf2 …… Kfn-1
> Kfn. Formation constants of Ni(II)
ammines, [Ni(NH3)n(H2O)6-n]2+
This trend is a result of the sequential n Kf Kn/Kn-1 Kn/Kn-1
decrease in number of H2O to be Exp Stat
replaced. 1 525

Situations do arise where Kfn > Kfn-1 2 148 0.28 0.42

Generally there are 2 reasons to
3 45.7 0.31 0.53
account for anomalies in the trends of
successive Kf values: 4 13.2 0.29 0.56

1  due to a major change in 5 4.7 0.35 0.53

electronic structure of the complex, e.g.
6 1.1 0.20 0.42
moving from a high spin (due to weak
field H2O) to a low spin complex.

2  due to a major structural change e.g. from an octahedral to a tetrahedral

or square planar geometry  characteristic of some halo complexes
Q. Consider the formation constants of the following Fe(II) complexes: Justify
the observed trend?

[Fe(bipy)(H2O)4]2+: Kf1: 4.2

[Fe(bipy)2(H2O)2]2+: Kf2: 3.7
[Fe(bipy)3]2+: Kf3: 9.3

Kf3: [Fe(bipy)3]2+ >> Kf2: [Fe(bipy)2(H2O)2]2+:

The reason is due to a major electronic shift 

from a high spin (due to weak field H2O) t2g4eg2 (LFSE Δo = 0.4) config 

to a low spin t2g6 config (CFSE Δo = 2.4). Large increase Δo.

Therefore [Fe(bipy)3]2+ is more stable than [Fe(bipy)2(H2O)2]2+

Q. Justify the following observation in the successive formation constants for
complexes of cadmium with Br-:
[Cd(Br)(H2O)5]+: Kf1: 36.3
[Cd(Br)2(H2O)4]: Kf2: 3.47
[Cd(Br)3(H2O)3]-: Kf3: 1.15
[Cd(Br)4]2-: Kf4: 2.34

The anomaly here is that Kf4: > Kf3:

The reason may not be electronic since both H2O and Br- are considered weak
field ligands

The reason is due to a major structural shift from an octahedral

[Cd(Br)3(H2O)3]- configuration 

to a tetrahedral [Cd(Br)4]2- geometry with the simultaneous expulsion of 3

molecules of water from a restricted geometry

Most halo complexes of M2+ have tetrahedral or square geometry

 Stepwise formation constants
These formation constants provide valuable information given that different species may
have VERY DIFFERENT properties…including environmental impact. Such information
provides selective isolation of metal ions from solution through reaction with ligands.

For formation of divalent alkaline earth

and 3d M2+ TM ions the Irving-
Williams Series holds true.

Ba<Sr<Ca<Mg<Mn<Fe<Co<Ni<Cu>Zn

What is contributing to this trend?

1. Charge to radius ratio.

2. CFSE (beyond Mn2+)
Jahn-Teller Distortion
3. Hard-Soft Acids/Bases
 Irving-Williams series

The stability order of complexes formed by divalent

3d transition metal ions.

Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+

Ca(II) Sc(II) Ti(II) V(II) Cr(II) Mn(II) Fe(II) Co(II) Ni(II) Cu(II) Zn(II)
d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
CFSE: 0 0.4Δ 0.8Δ 1.2Δ 0.6Δ 0 0.4Δ 0.8Δ 1.2Δ 0.6Δ 0

This pattern of variation in CFSE leads to greater stabilization in the complexes

of metal ions with high CFSE, such as Ni(II), and lower stabilization for the

complexes of M(II) ions with no CFSE, e.g. Ca(II), Mn(II), and Zn(II)
The Irving-Williams series summarises the relative stabilities of complexes
formed by M2+ ions.

The series reflect a combination of electrostatic effects and CFSE.

For the series Ba2+ < Sr2+ < Ca2+ < Mg2+ the observed trend is purely
electrostatic.

For the TMs in addition to electrostatic effects, the high values of Kf is due to
additional stability from CFSE.
In terms of ionic radii 

Mn2+ > Fe2+ > Co2+ > Ni2+ > Cu2+ > Zn2+

But, generally for strong field ligands the observed order is:

Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+

The additional stability of d9 Cu(II) is due to the influence of Jahn-Teller

distortion  results in the strong binding of the 4 planar ligands in
tetragonally distorted Cu(II) complexes  higher Kf values.
 Jahn-Teller Effect
Spontaneous loss of degeneracy of eg and t2g orbitals
for certain dn configurations

Cu2+

Octahedral Tetragonal

Some metal ions (e.g. Cu(II), d9 and Cr(II), high-spin d4) attain enhanced
electronic stability when they adopt a tetragonally distorted Oh geometry
rather than a regular Oh geometry.

They therefore undergo a spontaneous tetragonal distortion (Jahn-Teller

effect).

The net stabilization of the eg electrons for Cu(II), is shown above.

 Jahn-Teller Effect
N H2
10 en en
M2+ + L ↔ ML2+ (K1) gly
N H2

8 NH 2
gly
_
log K 1 ox O O

6 O O
_
ox
_
O O
mal
4 _
O
O
mal _
2 O
O
Mn Fe Co Ni Cu Zn

Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn 2+

dn d5 d6 d7 d8 d9 d10
LFSE (∆o) 0 2/5 4/5 6/5 3/5 0