Crystal Field Theory

Model for bonding in transition metal

complexes
Accounts for observed properties of transition
metal complexes
Focuses on d-orbitals
Ligands = point negative charges
Assumes ionic bonding
electrostatic interactions
Octahedral Complexes
Crystal Field Theory
Electrostatic Interactions
(+) metal ion attracted to (-) ligands (anion or
dipole)
provides stability
lone pair electrons on ligands repulsed by
electrons in metal d orbitals
interaction called crystal field
influences d orbital energies
not all d orbitals influenced the same way
d
x
2
-y
2
d
z
2
X
Y
Z
Y Z
Z
X
greater electrostatic repulsion = higher potential energy
Lobes directed at ligands
Crystal Field Theory
d
xy
d
xz
d
yz
X X Y
less electrostatic repulsion = lower potential energy
Lobes directed between ligands
Crystal Field Theory

Crystal Field Splitting Energy

determined by metal
ion and ligand
d
z
2
d
yz
d
xz
d
xy
d
x
2
- y
2
Strong Field and Low Spin
The splitting of d orbital energies explains the
color and magnetism of complex ions.
If the splitting produced by the ligands is very
large, a situation called strong field case, the
electrons will pair in the low energy t
2g
orbitals.
The strong field case is also called low spin case.
This gives a diamagnetic complex in which all
electrons are pairs.

o
> P
Weak Field and High Spin
If the splitting produced by the ligands is
small, the electrons will occupy all five
orbitals before pairing occurs called weak
field case.
The weak field case is also called high spin
case.
In this case, the complex is paramagnetic

o
< P
Octahedral transition-metal ions with d
1
, d
2
, or d
3
configurations
Octahedral transition-metal ions with d
4
, d
5
, d
6
, and d
7
configurations
For octahedral d
8
, d
9
, and d
10
complexes, there is
only one way to write satisfactory configurations.
weak fieldcase strong field case
with paramagnetic with diamagnetic
The Color of Complexes
Very commonly for the first transition
series, the energy corresponds to that
of visible light, so that d-d transitions
are the cause of the delicate colours of
so many of the complexes.
Crystal Field Theory
Can be used to account for
Colors of transition metal complexes
A complex must have partially filled d subshell on
metal to exhibit color
A complex with 0 or 10 d e
-
s is colorless
Magnetic properties of transition metal complexes
Many are paramagnetic
# of unpaired electrons depends on the ligand
Colors of Transition Metal Complexes
Compounds/complexes that have color:
absorb specific wavelengths of visible light
(400 700 nm)
wavelengths not absorbed are transmitted
Visible Spectrum
White = all the colors (wavelengths)
400 nm
700 nm
wavelength, nm
higher energy lower energy
(Each wavelength corresponds to a different color)
Visible Spectrum
Colors of Transition Metal Complexes
Compounds/complexes that have color:
absorb specific wavelengths of visible light (400
700 nm)
wavelengths not absorbed are transmitted
color observed = complementary color of color
absorbed
absorbed
color
observed
color
Absorption of UV-visible radiation by atom,
ion, or molecule:
Occurs only if radiation has the energy needed
to raise an electron from its ground state to an
excited state
i.e., from lower to higher energy orbital
light energy absorbed = energy difference between
the ground state and excited state
electron jumping
Different complexes exhibit different colors
because:
color of light absorbed depends on
larger = higher energy light absorbed
Shorter wavelengths
smaller = lower energy light absorbed
Longer wavelengths
magnitude of depends on:
ligand(s)
metal
Colors of Transition Metal Complexes
Charge Effect of Metal Ions
As the metal ion charge increases, the
ligands are drawn closer to the metal ion
because of its increased charge density.
As the ligands move closer, they cause
greater splitting of the d orbitals, thereby
producing a larger value.
The magnitude of for a given ligand
increases as the charge on the metal ion
increases.
NH
3
-Co
+2
(weak field) NH
3
-Co
+3
(strong field)
N
OH
pyr: pyridine phen: phenol
I
-
< Br
-
< CN
-
~ Cl
-
< F
-
< OH
-
~ NO
-
< C
2
O
4
2-
< H
2
O <
CS
-
< EDTA
4-
< NH
3
~ pyr ~ en < phen < CN
-
~ CO
Mn
2+
< Ni
2+
< Co
2+
< Fe
2+
< V
2+
< Fe
3+
< Co
3+
< Mn
3+
<
Co
3+
< Rh
3+
< Ru
3+
< Pd
4+
< Ir
3+
< Pt
4+
Spectrochemical Series
Spectrochemical Series
I
-
< Br
-
< Cl
-
< OH
-
< F
-
< H
2
O < NH
3
< en < CN
-
weak field
strong field
Smallest
Largest
increases
Colors of Transition Metal Complexes
Energy Splitting of Tetrahedral Complex
Because a tetrahedral complex has fewer
ligands, the magnitude of the splitting is
smaller.
The difference between the energies of the t
2g
and e
g
orbitals in a tetrahedral complex (
t
) is
slightly less than half as large as the splitting in
analogous octahedral complexes (
o
)

t
= 4/9
o
Square Planar and Linear Complex
The crystal field theory can be extended to square-
planar complexes, such as Pt(NH
3
)
2
Cl
2
.
Ligand Field Theory
Ligand field theory can be considered an
extension of crystal field theory such that
all levels of covalent interactions can be
incorporated into the model.
Treatment of the bonding in LFT is
generally done using molecular orbital
theory.
The Effect of Weak Field Ligands
A ligandwith a electronegative donor atom
will have lone pair orbitals of very low
energy (the electrons are very firmly bound
to the ligand); these orbitals do not mix
very thoroughly with the metal ion orbitals.
This will result in a small difference
between the t
2g
and e
g
*
orbitals.
The Effect of Strong Field Ligands
The strong field ligands produce larger
degree of mixing between the orbitals of
ligands and metal ions
This gives a relatively large amount of d-
orbital splitting, and low spin case results.
Biological Importance of Coordination
Complexes Hemoglobin
The principal electron transfer molecules in the
respiratory chain are iron-containing species
called cytochromes, consisting of two main part:
an iron complex called heme and a protein.
A metal ion coordinated to a rather complicated
planar ligandis called a porphyrin.
The various porphyrinmolecules act as
tetradentateligandsfor many metal ions,
including iron, cobalt and magnesium
heme
complex
Chlorophyll
Myoglobin
Iron plays a principal role in the transport and
storage of oxygen in mammalian blood and
tissues.
Oxygen is stored using a molecule called
myoglobin, which contains a hemecomplex and a
protein.
In myoglobin, the Fe
+2
ion is coordinated to four
nitrogen atoms of porphyrinring and to one
nitrigenatom of the protein chain.
Since Fe
+2
ion is normally six-coordinate, this
leaves one position open for attachment of an O
2
molecule.
Myoglobinmolecule
Hemoglobin
The transport of O
2
in the blood is
carried out by
hemoglobin, a
molecule consisting
of four myoglobin
molecules units.
Coordination Environment of Fe
2+
in
Oxymyoglobin and Oxyhemoglobin
N
Fe
N
N
N
O
2
N
NH
globin
(protein)
Bright red due to absorption
of greenish light
Strong field
Arterial Blood
large
N
Fe
N
N
N
OH
2
N
NH
globin
(protein)
Bluish color due to
absorption of orangish light
Weak field
Venous Blood
small