INORG A NI C C H EM I S T RY I I

P AR TA M E N TO D E Q U ÍM IC A
DE
UNIVERSIDAD DEL VALLE –
PROFESOR: RENSO VISBAL
a l@ co rre o u niv a lle .e du .co
EMAIL: renso.visb
 Tutorías
Lunes : 10-12
Miércoles : 15-17
Inorganic Chemistry, Shiver & Atkins

METHODOLOGY
Inorganic Chemistry, K. Housecroft
Physical Inorganic Chemistry, Kettle

Estudio propio por parte del estudiante¡¡

 EVALUATION

➢ 4 Exámenes parciales (Todo el temario)

➢ Se elimina la nota más baja y se toman las notas de los
tres exámenes restantes
➢ Los tres exámenes que se toman tienen el mismo
porcentaje (%)
 OCTAHEDRAL COMPLEXES

a) Octahedron b) Octahedral complex

Molecular Orbital Theory

OCTAHEDRAL COMPLEXES

Symmetry Elements
 OCTAHEDRAL COMPLEXES
Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh 6σd
Interacciones σC4Metal-Ligando
2

A1g 1 1 1 1 1 1 1 1 1 1 x 2 + y 2 + z2

A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 2z2 - x2 - y2, x2 – y2

T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)

T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)

A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)

T2u 3 0 1 -1 -1 -3 1 0 1 -1

Character table of point group Oh

 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

➢ Only orbitals of the same symmetry type have non-zero

overlap integrals.

➢ If there are two sets of orbitals of Eg symmetry, (one on

the ligands, the other on the metal), they will in general
be non-orthogonal (i.e. have a non-zero overlap
integral) and therefore interact.

➢ On the other hand both will have a zero overlap integral

with all orbitals of A1g, T1u, T2g and all other symmetry
species, wherever these are located in the molecule,
and will not interact with them..

General considerations
 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

s Because the 4s orbital of the central metal is turned

into itself by all the operations of the group
+ “multiplied by 1” its behaviour is described by the A1g
M irreducible representation of the character table

x y

The Metal s orbital

 OCTAHEDRAL COMPLEXES
Oh E 8C3 6C2 6C4 3C2 i 6S4 8S6 3σh 6σd
Interacciones σC4Metal-Ligando
2

A1g 1 1 1 1 1 1 1 1 1 1 x 2 + y 2 + z2

A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 2z2 - x2 - y2, x2 – y2

T1g 3 0 -1 1 -1 3 1 0 -1 -1 (Rx, Ry, Rz)

T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)

A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)

T2u 3 0 1 -1 -1 -3 1 0 1 -1

Character table of point group Oh

 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

The set of three 4p orbitals have T1u symmetry

The metal px, py and pz orbitals

 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

The five 3d orbitals split into two sets, of T2g and Eg

The metal dxy, dyz and dzx orbitals (T2g symmetry)

 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

The metal dx2-y2 and dz2 orbitals (Eg symmetry)

 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions
Symmetry Ligand Group Orbitals
1 We talk of the wavefunctions of various sets of ligand
a1g (σ 1 + σ 2 + σ 3 + σ 4 + σ 5 + σ 6 ) orbitals rather than of the wavefunctions corresponding
6
to individual ligand orbitals. The members of the
symmetry-classifiable sets are linear combinations of
1
t1u ⎧
⎪ (σ 1 − σ 6 ) the ligand σ orbitals and are often referred to either as
2
⎪
⎪ 1
'ligand group orbitals' or 'symmetry-adapted
⎨ (σ 2 − σ 4 ) combinations’.
⎪ 2
⎪ 1
(σ 3 − σ 5 )
⎪
⎩ 2 The step of moving from the individual ligand σ orbitals
to their “symmetry-adapted combinations” involves the
eg ⎧1 use of group theoretical procedures
⎪⎪2 (σ 2 − σ 3 + σ 4 − σ 5 )
⎨ 1
⎪ (2σ 1 + 2σ 6 − σ 2 − σ 3 − σ 4 − σ 5 )
⎪⎩ 2

Ligand group orbitals of six octahedrally-orientated

 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions
The labels σ1 → σ2 as shown in the figure.

In the explicit forms given in the table it has been

assumed that in the ligand a orbitals do not overlap
each other.

The ligand σ group orbitals listed in the table are of A1g,

Eg and T1u symmetries and each set will overlap with
metal orbitals of the same symmetries, so that the
4s(a1g), 4p(t1u) and 3d(eg) orbitals of the metal will be
involved in a bonding.

Of the valence shell orbitals of the metal atom only the

3d(t2g) orbitals are not involved in this bonding

The numbering system adopted for the ligand σ orbitals in an

octahedral complex
 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

The interactions of A1g, T1u and Eg symmetries are

shown pictorially in the next figures, where it can be
seen that there is the expected close matching between
ligand group orbitals and the corresponding metal
orbitals.

The metal-ligand σ bonding in an octahedral complex involving orbitals

of A1g symmetry. The metal σ orbital is shown at the centre
 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

If symmetry had not been applied to the σ

bonding problem then we would have had to
consider the interaction between the six
ligand σ orbitals and nine metal orbitals.

The interaction involving the metal px orbital is shown (with T1u

symmetry); there are similar interactions involving Py and Pz orbitals
 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

The interaction (a) between metal dx2-y2 and (b) dz2

orbitals and the corresponding ligand group orbitals
 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

The example shown is appropriate to a

d 7 ion in a strong-field (low-spin)
complex.

Electrons which, before the interactions

were 'switched on', were in pure ligand
orbitals are really in delocalized
molecular orbitals which take them onto
the metal atom the electron density on
the metal atom is increased as a result
of the covalency.

A schematic molecular orbital energy level scheme for an octahedral

complex of a first row transition metal ion (only σ interactions are included)
 OCTAHEDRAL COMPLEXES
Metal-Ligand σ Interactions

the d electrons of the uncomplexed

metal ion may be regarded as being
distributed between the t2g and eg (2)
molecular orbitals.

In the figure, Δ, the label given to the

energy separation between a lower t2g
and an upper eg set, is an experimental
quantity.

A schematic molecular orbital energy level scheme for an octahedral complex of a first
row transition metal ion (only σ interactions are included)
 OCTAHEDRAL COMPLEXES
Metal-Ligand π Interactions

π bonding appears to be generally true in

chemistry that π is rather weaker than σ
bonding. Thus, there is no compound known in
which it has been established that, in the
ground state, there is a π bond but no σ bond.

Each ligand has two orbitals available for π

bonding on each ligand-ligand px orbitals or
(ligand) molecular orbitals with the same
symmetry characteristics as the corresponding
px orbitals.

Ligand π orbitals in an octahedral complex. The arrow heads represent the lobe of
each orbital which has positive phase.
 OCTAHEDRAL COMPLEXES
Metal-Ligand π Interactions
Ligand group orbital Ligand group orbital
The symmetry-adapted 1 (π + π + π + π ) 1 (π + π - π - π )
combinations consist of four 2 2z 3z 4z 5z
2 2x 3y 4x 5y

sets with three ligand group t1u 1 (π + π + π + π ) t2g 1 (π + π - π - π )

2 1x 2x 6x 4x
2 1y 3z 6x 4x
orbitals in each set. The
1 (π + π + π + π ) 1 (π + π - π - π )
sets have T1g, T1u, T2g and 2 1y 3y 6y 5y
2 1x 2z 6y 5z

T2u symmetries. Simmetry

1 (π - π - π + π ) 1 (π - π + π - π )
2 2x 3y 4x 5y
2 2z 3z 4z 5z

There are no metal orbitals t1g 1 (π - π - π + π ) t2u 1 (π - π + π - π )

of T1g and T2u symmetries 2 1x 2z 6y 4z
2 1x 2x 6x 4x

1 (π - π - π + π ) 1 (π - π + π - π )
within our chosen valence 2 1y 3z 6x 5z
2 1y 3y 6y 5y

set.

π ligand group orbitals for the six ligands in octahedral complexes

 OCTAHEDRAL COMPLEXES
Metal-Ligand π Interactions

The ligand π group orbitals ofT1g and T2u symmetries

are therefore carried over, unmodified, into the full
molecular orbital description.

a) One of the three ligand π group orbitals of T1g symmetry.

b) One of the three ligand π group orbitals of T2u symmetry.
 OCTAHEDRAL COMPLEXES
Metal-Ligand π Interactions

The T1u set will interact with the metal p

orbitals (also of T1u symmetry).

Notice that of the 12 π ligand orbitals only

four are involved in this particular
combination. The remaining eight similarly
divide into two sets of four, with no
member common to any two sets.

Case 1: The ligand π orbitals are occupied

OCTAHEDRAL COMPLEXES
Metal-Ligand π Interactions

Interaction with the t1u(1) molecular

orbitals will raise or lower this latter
set depending on whether its energy is
higher or lower than that of the ligand
π (T1u) set.

Case 1: The ligand π orbitals are occupied

 OCTAHEDRAL COMPLEXES
Metal-Ligand π Interactions

Interaction between the ligand π and

(occupied) t1u(1) sets of Figure a will
result in a repulsion between the two and
the t1u(1) set will be stabilized somewhat
but the orbital occupancy will remain
unchanged.

Case 2: The ligand π orbitals are unoccupied

 OCTAHEDRAL COMPLEXES
Metal-Ligand π Interactions

Halides

CN-

If the ligand π set is the higher in energy then the metal t2g set is
pushed down; if the ligand π set is the lower, the metal set is raised
in energy. The magnitude of Δ depends, in part, on π bonding

(a) The interaction between a metal t2g orbital (dxy). (b) The consequences when the ligand π(t2g)
are low lying (occupied). (c) The consequences when the ligand π(t2g) are high lying (empty).
 TETRAHEDRAL COMPLEXES

If Cartesian axes are drawn

as in figures then x ≡ y ≡ z so
that dxy, dyz and dzx must be
degenerate.

The degeneracy of dx2-y2 and

dz2 follows just as it did for
octahedral complexes.

Metal d orbitals in a tetrahedral complex

 TETRAHEDRAL COMPLEXES
Symmetry
Simetria Ligand Group del
Grupo orbital Orbitals
ligando
1
a1 (σ 1 + σ 2 + σ 3 + σ 4 )
2
⎧1
⎪ 2 (σ 1 + σ 2 − σ 3 − σ 4 )
⎪
⎪1
t2 ⎨ (σ 1 − σ 2 − σ 3 + σ 4 )
⎪2
⎪1
⎪ 2 (σ 1 − σ 2 + σ 3 − σ 4 )
⎩

The labels used in the text for the ligand u orbitals of a tetrahedral complex
 TETRAHEDRAL COMPLEXES

(a) Interaction of the ligand a1 group orbital with the metal s orbital. (b) Interaction of
the first ligand t2 σ group orbital with the corresponding metal p orbital
 TETRAHEDRAL COMPLEXES

The ligand σ electrons are stabilized by

interaction with the corresponding metal
orbitals. The (three) electrons originally in the
metal d orbitals correspond with those
distributed between the e(1) and t 2 (2)
molecular orbitals

A schematic molecular orbital energy level diagram for tetrahedral complexes with
only σ interactions included
 TETRAHEDRAL COMPLEXES

On each ligand there are two π orbitals and these

may be regarded as lying in a plane perpendicular to
the local ligand-metal axis (at each ligand this plane
is represented by a circle which. However, may
appear as an ellipse because of the perspective).

At each ligand an orbital is labelled πv if it lies in a

plane containing the z axis and πh if it is
perpendicular to this plane.

A symbolic representation of the ligand π orbitals in a tetrahedral complex

 TETRAHEDRAL COMPLEXES

Ligand π group orbitals of E symmetry: (a) that which overlaps with the metal
dz2; (b) that which overlaps with the metal dx2-y2
 TETRAHEDRAL COMPLEXES

A ligand π group orbital of T2 symmetry together with the metal pz with which it overlaps
 TETRAHEDRAL COMPLEXES
Symmetry Ligand Group Orbitals

For tetrahedral complexes π bonding

involves all of the metal d orbitals, not just
one set (as in the octahedral case), and it
is not possible to give a simple diagram
analogous

π ligand group orbitals of a tetrahedral complex

 TETRAHEDRAL COMPLEXES

Because all of the σ metal orbitals are

affected by the presence of π
interactions, the molecular orbital diagram,
and hence the Δ is not quite simple to
explain

A schematic molecular orbital energy level diagram for a tetrahedral transition metal 4p
complex in which both σ and π interactions are important
COMPLEXES OF OTHER GEOMETRIES
COMPLEXES OF OTHER

GEOMETRIES
COMPLEXES OF OTHER

GEOMETRIES
 COMPLEXES OF OTHER GEOMETRIES

may each interact with either or both of

The two ligand s orbitals of A1' symmetry:
the metal orbitals of A1' symmetry:

Ligand Metal

σ bonding in a D3h complex

 COMPLEXES OF OTHER GEOMETRIES

Similarly, the ligand A2" σ orbital interacts and the ligand e' orbitals interact with the
with the metal pz orbital metal px orbitals:

σ bonding in a D3h complex

 COMPLEXES OF OTHER GEOMETRIES

and the ligand e' orbitals interact with metal py orbitals:

σ bonding in a D3h complex