Reactions and Stability of

Coordination Compounds

Complexes undergo various types of reactions:

• Insertion
• Oxidative addition
• Substitution of ligands (ligand exchange)
• Electron transfer (redox)

Of these, ligand exchange and redox are the most common

types of reactions. We will focus on ligand exchange only.
 Ligand Exchange Mechanisms

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

H2O is the leaving ligand and NH3 is the entering ligand.

 Ligand Exchange Mechanisms

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

A ligand exchange reaction proceeds via an intermediate

state. It occurs via three mechanisms, depending on the
type of intermediate complex:

• Associative
• Interchange
• Dissociative
 Stability of Coordination
Compounds
The stability of a coordination compound can be interpreted
in two ways:

• Thermodynamic stability: the extent to which the

forward reaction is favoured.

• Kinetic stability: the rate at which equilibrium is attained.

Is related to the reactivity of a complex.
 Thermodynamic
Stability
Thermodynamic stability can be quantitatively described by
the stability constant.

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

 The Stability Constant

The four ligands are replaced in a stepwise fashion:

Step 1: [Cu(H2O)6]2+ + NH3 ⇋ [Cu(H2O)5(NH3)]2+ + H2O

Step 2: [Cu(H2O)5(NH3)]2+ + NH3 ⇋ [Cu(H2O)4(NH3)2]2++ H2O

Step 3: [Cu(H2O)4(NH3)2]2+ + NH3 ⇋ [Cu(H2O)3(NH3)3]2++ H2O

 The Stability Constant

The calculated value of each stability constant is given in the table

below. It is easier to interpret log Kn.

Complex Ion Kn Value log Kn

[Cu(H2O)5(NH3)]2+ K1 1.78  104 4.25
[Cu(H2O)4(NH3)2]2+ K2 4.07  103 3.61
[Cu(H2O)3(NH3)3]2+ K3 9.55  102 2.98
[Cu(H2O)2(NH3)4]2+ K4 1.74 102 2.24

The overall stability constant () is the product of Kn:

 = K1  K2  K3  K4 = 1.20  1013
 The Stability Constant

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

The large overall stability constant ( = 1.20  1013) is large.

This means the equilibrium lies far to the right. In other
words, the formation of the new complex [Cu(H2O)2(NH3)4]2+
is favoured and therefore thermodynamically stable.
 Thermodynamic Stability

Factors that influence the stability of a complex:

1) Properties of the metal ion – charge, size, electronegativity,

hard or soft acid.
2) Ligand properties – size, charge, chelate effect, steric effects,
basic character

Each of these factors is discussed briefly hereafter.

 Thermodynamic Stability

1) Properties of the metal ion

• In general metal ions with higher charge and small size (i.e. high charge
density) form stable complexes since they attract the ligands more
closely leading to stable complexes.
• Metals with small size and high charge are called hard acids. They are
easily polarizable (i.e. their electron clouds are easily distorted in the
presence of another charged particle). Examples are Group I – III
metals, Ti4+, Cr6+). Soft acids are bigger and have lower oxidation states
(e.g. Ni0, Cu+, Ag+, Cd2+)
• A metal with a high tendency to attract an electron pair (higher
electronegativity) form more stable complexes.
 Thermodynamic Stability

2) Properties of the ligand

• Ligands are classified as hard bases and soft bases - hard bases
are small, polarizable donor atoms. They include H2O, OH-, O2-,
NO3-, Cl-, F- and NH3. Soft bases include H-, CO, CN-, PR3, R2S
(where R = alkyl group)

The rule is “like binds like”. In other words, a hard acid bonded to
a hard base, or a soft acid bonded to a soft base improves
stability. This is called Hard-Soft-Acid-Base (HSAB) Theory.
 Thermodynamic Stability

2) Properties of the ligand (continued) – the chelate effect

Remember that a polydentate ligand binds to the metal center

simultaneously via more than one donor atom. Complexes
that contain chelates (or polydentate ligands) are more stable
than those with monodentate ligands.
 Thermodynamic Stability
Worked Example 1:
Which of the following ions will have the greater stability: [AuF2]- or [AuI2]-?
Give your reasoning.

Solution:
Au+ has a small charge-to-radius ratio (the charge is only 1+ and it has a
large radius). According to literature its charge density is only 11. It can
therefore be classified as a “soft” acid.

F- (2 energy levels) is much smaller than I- (5 energy levels) and is therefore

a “hard” base and will not bind as strongly to the “soft” Au center as the
“soft” I- .
 Thermodynamic Stability

Worked Example 2:

Copper(I) iodide is known, but copper(II) iodide is not. Explain.

Solution:

The iodide ion is a “soft” base. Cu+ is a “soft” acid. Therefore CuI
is more likely to form than CuI2 .
 Stability and Reactivity

• A complex may be stable (high stability constant) yet have high reactivity
(fast ligand exchange rate).

• For example, [Ni(CN)4]2- has a high stability constant (Kf = 1.3  1030). Yet,
the complex exchanges CN- rapidly in solution (k2 > 5  105 M-1s-1).
[Ni(CN)4]2- is therefore thermodynamically stable, but not kinetically
stable. This reactivity is attributed to its square planar geometry.

• The reactivity of a complex depends on its activation energy only – in

other words the energy “hump” that must be overcome before products
are formed.
 Labile and Inert Complexes

Complexes that exchange ligands rapidly (fast) are termed

labile, meaning the metal-ligand bond is easily broken.
Complexes that exchange ligands slowly are termed inert.
 Labile and Inert Complexes

Factors that influence lability:

• Charge of the central ion: Highly charged ions form complexes

which react slowly, i.e. inert.
• Radius of the ion: the reactivity decreases with decreasing
ionic radii.
• Charge to radius ratio: if all the factors are similar, the ion with
largest Z/r value reacts with the least rate.
• Geometry of the complex: Generally four coordinated
complexes are more labile
 Labile and Inert Complexes

Worked Example 3
Which of the following complexes would exchange NH3 ligands at the
slowest rate in aqueous solution: [Co(NH3)6]2+ or [Co(CN)(NH3)5]2+

Solution
In the first complex the oxidation state of Co is 2+ and in the second
complex it is 3+. Therefore [Co(CN)(NH3)5]2+ will react slower.
 Labile and Inert Complexes

Worked Example 4
Which of the following complexes is more labile (i.e. would
exchange ligands fastest): [Cr(en)2Cl4]- or [Cu(en)2Cl4]2-

Solution
Cu2+ is smaller than Cr3+ (Cu2+ has a larger Zeff!!!). Since reactivity
increases with increasing ionic radius, [Cr(en)2Cl4]- is more labile
than [Cu(en)2Cl4]2-.
 Labile and Inert Complexes
The rate at which a complex exchange ligands (i.e. its
kinetic stability) can be explained in terms of VBT and CFT.

• VBT is premised on the assumption that for an

entering ligand to bond with the metal centre, there
should be vacant (at best) or half-filled d-orbitals
available for bonding.
• CFT is premised on the idea that ligands are drawn via
electrostatic forces to the metal ion centre thereby
causing d-orbital splitting.
 Labile and Inert Complexes

Lability and inertness explained: Valence Bond Theory

VBT classifies octahedral complexes into two types:

• Inner orbital complexes, and

• Outer orbital complexes
 Labile and Inert Complexes

In inner orbital complexes the hybridization mode is written as

d2sp3 to show the d-orbitals involved are from the lower energy
level.
 Labile and Inert Complexes

In outer orbital complexes, the hybridization mode is written

as sp3d2 to show the d-orbitals involved are from the higher
energy level. Outer orbital complexes are normally high-spin
complexes.
 Labile and Inert Complexes

• Inner orbital complexes are normally diamagnetic (or less

paramagnetic) and are therefore low-spin complexes (e.g.
[Co(NH3)6]3+). Inner orbital complexes are mostly inert.

• Outer orbital complexes have weaker bonds and are

generally labile. Examples include Mn(II), Fe(II), Fe(III),
Co(II), Ni(II), Cu(II) and Cr(II). They are high-spin complexes
(e.g. [Co(F6)]3-)
 Labile and Inert Complexes

Lability and inertness explained: Crystal Field Theory

Metals like Ni2+ (t2g6 eg2) and Cu2+ (t2g6 eg3) are very labile. And so
are Sc3+ and Ti4+. But, V2+ (t2g3 eg0) is inert.
• All complexes where the metal ion has electrons in the eg
orbitals, e.g. high spin Co2+ (d7: t2g5 eg2 ), high spin Fe3+ (d5: t2g3
eg2) and all complexes with less than three d-electrons, e.g.
Ti3+ (d1: t2g1 eg0 ) are labile.
• Octahedral d3 complexes are inert (e.g. Cr3+: t2g3 eg0 ) as well
as low spin d4 – d6 complexes, e.g. Co3+ (d6: t 6 e 0).
 Labile and Inert Complexes

Worked Example 5
Explain, using CFT, which of the following complexes is more labile
(i.e. would exchange ligands fastest): [Cr(en)2Cl4]- or [Cu(en)2Cl4]2-

Solution
Cu2+: t2g6 eg3
Cr3+: t2g3 eg0.
Therefore [Cu(en)2Cl4]2- is more labile than [Cr(en)2Cl4]-.
 Labile and Inert Complexes

Worked Example 6
Explain, using CFT, why [Fe(CO)6]2+ is more inert compared to
[Fe(OH)2].

Solution
In both compounds the oxidation state of Fe = 2+. However, the
first compound is a low spin complex (CO is a strong field
ligand) and has the t2g orbitals filled (t2g6 eg0) . The second
compound is high-spin since OH- is a weak field ligand (t2g4 eg2).