Coordination

Chemistry II
Bonding, including crystal
field theory and ligand field
theory

Basis for Bonding

Theories
Models for the bonding in
transition metal complexes must be
consistent with observed behavior.
Specific data used include stability
(or formation) constants, magnetic
susceptibility, and the electronic
(UV/Vis) spectra of the complexes.

Bonding Approaches
Valence Bond theory provides the
hybridization for octahedral complexes.
For the first row transition metals, the
hybridization can be: d2sp3 (using the 3d,
4s and 4p orbitals), or sp3d2 (using the 4s,
4p and 4d orbitals).
The valence bond approach isnt used
because it fails to explain the electronic
spectra and magnetic moments of most
complexes.

Crystal Field Theory

In crystal field theory, the
electron pairs on the ligands are
viewed as point negative charges
that interact with the d orbitals on
the central metal. The nature of the
ligand and the tendency toward
covalent bonding is ignored.

d Orbitals

Crystal Field Theory

Ligands, viewed as point charges,
at the corners of an octahedron
affect the various d orbitals
differently.

Crystal Field Theory

Crystal Field Theory

The repulsion
between ligand
lone pairs and
the d orbitals on
the metal results
in a splitting of
the energy of
the d orbitals.

d Orbital Splitting
__
__ e
g
dz2 dx2-y2
__ __ __ __ __

0.6o

Spherical field

0.4o

__
__ __t
2
dxy dxz dyz
g

Octahedral field

d Orbital Splitting
In some texts and articles, the
gap in the d orbitals is assigned a
value of 10Dq. The upper (eg) set
goes up by 6Dq, and the lower set
(t2g) goes down by 4Dq.
The actual size of the gap varies
with the metal and the ligands.

d Orbital Splitting
The colors exhibited by most
transition metal complexes arises
from the splitting of the d orbitals.
As electrons transition from the
lower t2g set to the eg set, light in the
visible range is absorbed.

d Orbital Splitting
The splitting due
to the nature of
the ligand can be
observed and
measured using a
spectrophotometer
. Smaller values
of o result in
colors in the green
range. Larger
gaps shift the
color to yellow.

The Spectrochemical
Series
Based on measurements for a given
metal ion, the following series has
been developed:
I-<Br-<S2-<Cl-<NO3-<N3-<F-<OH-<C2O42<H2O
<NCS<CH3CN<pyridine<NH3<en<bipy<phen
<NO2-<PPh3<CN-<CO

The Spectrochemical
Series
The complexes
of cobalt (III) show
the shift in color
due to the ligand.
(a) CN, (b) NO2,
(c) phen, (d) en, (e)
NH3, (f) gly, (g)
H2O, (h) ox2, (i)
CO3 2.

Ligand Field Strength

Observations
1. o increases with increasing
oxidation number on the metal.
Mn+2<Ni+2<Co+2<Fe+2<V+2<Fe+3<Co+
3

<Mn+4<Mo+3<Rh+3<Ru+3<Pd+4<Ir+3<Pt
+4

2. o increases with increases going

down a group of metals.

Ligand Field Theory

Crystal Field Theory completely ignores
the nature of the ligand. As a result, it
cannot explain the spectrochemical series.
Ligand Field Theory uses a molecular
orbital approach. Initially, the ligands can
be viewed as having a hybrid orbital or a p
orbital pointing toward the metal to make
bonds.

Octahedral Symmetry
http://www.iumsc.indiana.edu/morpho
logy/symmetry/octahedral.html

Ligand Field Theory

Consider the sigma bonds to all
six ligands in octahedral geometry.
Oh

3C2
6C 6C
6S 8S 3 6
E 8C3
(=C4 i
2
4
4
6
h
d
2
)

0 0

This reduces to A1g + Eg + T1u

Ligand Field Theory

The A1g group
orbitals have the
same symmetry
as an s orbital
on the central
metal.

Ligand Field Theory

The T1u group
orbitals have the
same symmetry as
the p orbitals on
the central metal.
(T representations
are triply
degenerate.)

Ligand Field Theory

The Eg group
orbitals have the
same symmetry as
the dz2 and dx2-y2
orbitals on the
central metal.
(E representations
are doubly
degenerate.)

Ligand Field Theory

Since the ligands
dont have a
combination with t2g
symmetry, the dxy,
dyz and dxy orbitals
on the metal will be
non-bonding when
considering
bonding.

Ligand Field Theory

The molecular
orbital diagram
is consistent with
the crystal field
approach.
Note that the t2g
set of orbitals is
non-bonding, and
the eg set of
orbitals is
antibonding.

Ligand Field Theory

The electrons
from the
ligands (12
electrons from
6 ligands in
octahedral
complexes)
will fill the
lower bonding
orbitals.

Ligand Field Theory

The electrons
from the 4s
and 3d orbitals
of the metal (in
the first
transition row)
will occupy the
middle portion
of the diagram.

Experimental Evidence for

Splitting
Several tools are used to confirm the
splitting of the t2g and eg molecular
orbitals.
The broad range in colors of transition
metal complexes arises from electronic
transitions as seen in the UV/visible
spectra of complexes.
Additional information is gained from
measuring the magnetic moments of the
complexes.

Experimental Evidence for

Splitting
Magnetic susceptibility

measurements can be
used to calculate the
number of unpaired
electrons in a
compound.
Paramagnetic
substances are
attracted to a magnetic
field.

Magnetic Moments
A magnetic balance can be used to
determine the magnetic moment of a
substance. If a substance has unpaired
electrons, it is paramagnetic, and attracted
to a magnetic field.
For the upper transition metals, the spinonly magnetic moment, s, can be used to
determine the number of unpaired
electrons.
s = [n(n+2)]1/2

Magnetic Moments
The magnetic moment of a
substance, in Bohr magnetons, can
be related to the number of unpaired
electrons in the compound.
s = [n(n+2)]1/2
Where n is the number of unpaired
electrons

Magnetic Moments
Complexes with 4-7 electrons in the
d orbitals have two possibilities for
the distribution of electrons. The
complexes can be low spin, in which
the electrons occupy the lower t2g set
and pair up, or they can be high spin.
In these complexes, the electrons
will fill the upper eg set before
pairing.

High and Low Spin

Complexes
If the gap between
the d orbitals is
large, electrons will
pair up and fill the
lower (t2g) set of
orbitals before
occupying the eg set
of orbitals. The
complexes are called
low spin.

High and Low Spin

Complexes
In low spin
complexes, the
size of o is
greater than the
pairing energy
of the electrons.

High and Low Spin

Complexes
If the gap between
the d orbitals is
small, electrons will
occupy the eg set of
orbitals before they
pair up and fill the
lower (t2g) set of
orbitals before. The
complexes are called
high spin.

High and Low Spin

Complexes
In high spin
complexes, the
size of o is less
than the pairing
energy of the
electrons.

Ligand Field
Stabilization Energy
The first row transition metals in
water are all weak field, high spin
cases.
do d1

d2

d3

d4 d d d7 d8
5

d9 d10

LFS 0 .
.8 1.2 .6 0 .4 .8 1.2 .6
E
4o

Experimental Evidence
for LFSE
The hydration energies of the first
row
transition metals should increase
across the period as the size of the
metal ion gets smaller.
M2+ + 6 H2O(l) M(H2O)62+

Experimental Evidence
for LFSE
The heats of
hydration show two
humps consistent
with the expected
LFSE for the metal
ions. The values for
d5 and d10 are the
same as expected
with a LFSE equal
to 0.

Experimental Evidence of
LFSE
do d1

d d3 d d d d7 d8 d9 d10
2

LFS 0 .
.8 1. . 0 .4 .8
E
4o
2 6

1. .6
2

High Spin vs. Low Spin

3d metals are generally high spin
complexes except with very strong
ligands. CN- forms low spin
complexes, especially with M 3+ ions.
4d & 4d metals generally have a larger
value of o than for 3d metals. As a
result, complexes are typically low
spin.

Nature of the Ligands

Crystal field theory and ligand field
theory differ in that LFT considers the
nature of the ligands. Thus far, we have
only viewed the ligands as electron
pairs used for making bonds with the
metal. Many ligands can also form
bonds with the metal. Group theory
greatly simplifies the construction of
molecular orbital diagrams.

Considering Bonding
To obtain red for bonding, a set
of cartesian coordinates is
established for each of the ligands.
The direction of the bonds is
arbitrarily set as the y axis (or the py
orbitals). The px and pz orbitals are
used in bonding.

x
x
z

z
y

y
y
x y
z
x

Oh E 8C3

1
2

z
y x
y x
z

6C 6C
2

Considering
Bonding
Consider only the
px and pz orbitals
on each of the
ligands to obtain
.
3C
2

(=C4 i
2
)
-4

6S 8S 3 6
4

0 0

Considering Bonding
Oh

3C2
6C 6C
6S 8S 3 6
E 8C3
(=C4 i
2
4
4
6
h
d
2
)
1
0
0
0
-4 0 0 0 0 0
2

This reduces to T1g + T2g + T1u + T2u. The T2g set

has the same symmetry as the d xy, dyz and dxz
orbitals on the metal. The T1u set has the same
symmetry as the px, py and pz orbitals on the
metal.

Considering Bonding
reduces to: T1g + T2g + T1u + T2u.

The T1g and T2u group orbitals for the ligands dont
match the symmetry of any of the metal orbitals.

The T1u set has the same symmetry as the px, py

and pz orbitals on the metal. These orbitals are
used primarily to make the bonds to the ligands.

The T2g set has the same symmetry as the dxy, dyz
and dxz orbitals on the metal.

 Bonding
The main source of bonding is
between the dxy, dyz and dxz orbitals
on the metal and the d, p or *
orbitals on the ligand.

 Bonding
The ligand may have empty d or
* orbitals and serve as a acceptor
ligand, or full p or d orbitals and
serve as a donor ligand.

 Bonding
The empty antibonding orbital
on CO can accept electron density
from a filled d orbital on the metal.
CO is a pi acceptor ligand.
empty *
filled
orbital
d
orbita
l

 Donor Ligands (L M)
All ligands are donors. Ligands
with filled p or d orbitals may also
serve as pi donor ligands. Examples
of donor ligands are I-, Cl-, and S2-.
The filled p or d orbitals on these
ions interact with the t2g set of
orbitals (dxy, dyz and dxz) on the metal
to form bonding and antibonding
molecular orbitals.

 Donor Ligands (L M)
The bonding orbitals,
which are lower in
energy, are primarily
filled with electrons
from the ligand, the
and antibonding
molecular orbitals are
primarily occupied by
electrons from the
metal.

 Donor Ligands (L M)
The size of o
decreases, since it is
now between an
antibonding t2g orbital
and the eg* orbital.
This is confirmed by the
spectrochemical series.
Weak field ligands are
also pi donor ligands.

 Acceptor Ligands
(M L)
Ligands such as CN,
N2 and CO have
empty
antibonding orbitals
of the proper
symmetry and
energy to interact
with filled d orbitals
on the metal.

 Acceptor Ligands
(M L)
The metal uses the
t2g set of orbitals (dxy,
dyz and dxz) to engage
in pi bonding with
the ligand. The *
orbitals on the ligand
are usually higher in
energy than the d
orbitals on the metal.

 Acceptor Ligands
(M L)
The metal uses the
t2g set of orbitals (dxy,
dyz and dxz) to engage
in pi bonding with
the ligand. The *
orbitals on the ligand
are usually higher in
energy than the d
orbitals on the metal.

 Acceptor Ligands
(M L)
The interaction
causes the energy
of the t2g bonding
orbitals to drop
slightly, thus
increasing the
size of o.

Summary
1. All ligands are donors. In general,
ligand that engage solely in
bonding are in the middle of the
spectrochemical series. Some very
strong donors, such as CH3- and Hare found high in the series.
2. Ligands with filled p or d orbitals
can also serve as donors. This
results in a smaller value of o.

Summary
3. Ligands with empty p, d or *
orbitals can also serve as
acceptors. This results in a larger
value of o.
I-<Br-<Cl-<F-<H2O<NH3<PPh3<CO
donor< weak donor< only< acceptor

4 Coordinate
Complexes
Square planar and tetrahedral
complexes are quite common for
certain transition metals. The
splitting patterns of the d orbitals on
the metal will differ depending on
the geometry of the complex.

Tetrahedral Complexes
The dz2 and dx2-y2 orbitals
point directly between
the ligands in a
tetrahedral
arrangement. As a
result, these two
orbitals, designated as
e in the point group Td,
are lower in energy.

Tetrahedral Complexes
The t2 set of orbitals,
consisting of the dxy, dyz,
and dxz orbitals, are
directed more in the
direction of the ligands.
These orbitals will be
higher in energy in a
tetrahedral field due to
repulsion with the
electrons on the ligands.

Tetrahedral Complexes
The size of the splitting,
T, is considerable smaller
than with comparable
octahedral complexes.
This is because only 4
bonds are formed, and the
metal orbitals used in
bonding dont point right
at the ligands as they do
in octahedral complexes.

Tetrahedral Complexes
In general, T
4/9 o. Since
the splitting is
smaller, all
tetrahedral
complexes are
weak-field, highspin cases.

Tetragonal Complexes
Six coordinate complexes, notably
those of Cu2+, distort from
octahedral geometry. One such
distortion is called tetragonal
distortion, in which the bonds along
one axis elongate, with compression
of the bond distances along the
other two axes.

Tetragonal Complexes
The elongation
along the z axis
causes the d
orbitals with density
along the axis to
drop in energy. As
a result, the dxz and
dyz orbitals lower in
energy.

Tetragonal Complexes
The compression
along the x and y
axis causes
orbitals with
density along
these axes to
increase in energy.
.

Tetragonal Complexes
For complexes
with 1-3 electrons
in the eg set of
orbitals, this type
of tetragonal
distortion may
lower the energy
of the complex.

Square Planar

Complexes

For complexes with 2

electrons in the eg set of
orbitals, a d8
configuration, a severe
distortion may occur,
resulting in a 4coordinate square planar
shape, with the ligands
along the z axis no
longer bonded to the
metal.

Square Planar

Complexes

Square planar
complexes are quite
common for the d8
metals in the 4th and 5th
periods: Rh(I), IR(I),
Pt(II), Pd(II) and Au(III).
The lower transition
metals have large ligand
field stabalization
energies, favoring fourcoordinate complexes.

Square Planar

Complexes

Square planar
complexes are rare for
the 3rd period metals.
Ni(II) generally forms
tetrahedral complexes.
Only with very strong
ligands such as CN-, is
square planar
geometry seen with
Ni(II).

Square Planar

Complexes

The value of sp
for a given metal,
ligands and bond
length is
approximately
1.3(o).

The Jahn-Teller Effect

If the ground electronic
configuration of a non-linear
complex is orbitally degenerate, the
complex will distort so as to remove
the degeneracy and achieve a lower
energy.

The Jahn-Teller Effect

The Jahn-Teller effect predicts
which structures will distort. It does
not predict the nature or extent of
the distortion. The effect is most
often seen when the orbital
degneracy is in the orbitals that
point directly towards the ligands.

The Jahn-Teller Effect

In octahedral complexes, the
effect is most pronounced in high
spin d4, low spin d7 and d9
configurations, as the degeneracy
occurs in the eg set of orbitals.
d4

d7

d9
eg

t2g

The Jahn-Teller Effect

The strength of the Jahn-Teller
effect is tabulated below: (w=weak,
s=strong)
1
#e

1 2 3 4 5 6 7 8 9

High
* * * s - w w * * *
spin
Low
w w - w w - s - s spin
*There is only 1 possible ground state
configuration.
- No Jahn-Teller distortion is expected.

Experimental Evidence of
LFSE
do d1

d d3 d d d d7 d8 d9 d10
2

LFS 0 .
.8 1. . 0 .4 .8
E
4o
2 6

1. .6
2