Coordination Chemistry III

Bonding, Ligand Field Theory

CYL101
DPM, IIT Ropar

Limitations of CFT
1. CFT consider only metal ion d-orbitals and gives no
consideration at all to other metal orbitals (Such as s, p
orbital).
2. CFT is unable to account satisfactorily for the relative
strengths of ligands for example it gives no explanation as
to why H2O is a stronger ligand than OH– in the
spectrochemical series.
3. According to CFT, the bond between the metal and ligands
are purely ionic. It gives no account on the partly covalent
nature of the metal-ligand bonds.
4. CFT cannot account for the p-bonding in complexes.

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 Ligand Field Theory (LFT)
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 Theory
approach. Initially, the ligands can be viewed as having a
hybrid orbital or a p orbital pointing toward the metal to
make σ bonds.

Same as previous use of MO theory, build ligand group

orbitals, combine them with metal atomic orbitals of matching
symmetry to form MO’s.

Octahedral Complexes
1. History
 Crystal Field Theory only includes ionic interactions in the solid state
 MO Theory developed and applied only to non-metal compounds
 Ligand Field Theory combines both (CFT & MOT) for transition metal
coordination compounds

2. MO’s for Oh complexes

 Donor atom = atom in the ligand with a p-orbital or hybrid orbital
directly approaching the metal ion to form a σ-bond
 The dxy, dxz, dyz orbitals are not of correct symmetry to σ-bond
with ligands
 The dx2–y2, dz2, px, py, pz, and s orbitals all have correct symmetry
for interaction with ligands

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 Bonding Interactions d-orbitals

z z

x x

Non-Bonding (No
interaction) 4 ligand orbitals
and metal dxy orbitals

Note: σ-bond require head-on interaction

σ σ π

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 Symmetry Labels for Configurations

 Symmetry labels for electron configurations

match their degeneracies.
 T = triply degenerate asymmetrical state
 E = doubly degenerate asymmetrical state

 A or B = nondegenerate

Ligand Field Theory

Approach of Ligands
Consider the sigma bonds to all six ligands in octahedral geometry.

3C2
Oh E 8C3 6C2 6C4 i 6S4 8S6 3σh 6σd
(=C42)
Γσ 6 0 0 2 2 0 0 0 4 2

This reduces to A1g + Eg + T1u

6 ligands = 6 orbitals (1 + 2 +3)

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 Ligand Field Theory
Combination of Metal and Ligand orbitals

The A1g group orbitals have

the same symmetry as an s
orbital on the central metal.

Ligand have (A1g + Eg + T1u)

Ligand Field Theory

Combination of Metal and Ligand orbitals

The ligand T1u group orbitals

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

Ligand have (A1g + Eg + T1u)

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 Ligand Field Theory
Combination of Metal and Ligand orbitals

The ligand Eg group orbitals

have the same symmetry as the
dz2 and dx2–y2 orbitals on the
central metal.

(E representations are doubly

degenerate.)

Ligand have (A1g + Eg + T1u)

Ligand Field Theory

Combination of Metal and Ligand orbitals

Since the ligands don’t have a

combination with t2g symmetry,
the dxy, dyz and dxy orbitals on
the metal will be non-bonding
when considering σ bonding.

Ligand have (A1g + Eg + T1u)

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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 have (A1g + Eg + T1u)

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.

The electrons from the

ligands (12 electrons from 6

}
ligands in octahedral
complexes) will fill the lower
bonding orbitals.

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Use the Group Theory Approach to find Molecular Orbitals
1. The six ligand orbitals generate the group orbitals to combine with
metal Atomic Orbitals
2. The reducible representation: G = A1g + T1u + Eg
3. Nondbonding metal orbitals: dxy, dxz, dyz orbitals have T2g
symmetry
4. Bonding metal orbitals: s orbital has A1g symmetry; px, py, pz
have T1u symmetry, and dx2–y2, dz2, have Eg symmetry.
5. The 6 metal AO’s of proper symmetry combine with the six
ligand group orbitals
6. 6 bonding MO’s are filled by ligand electron pairs
7. The metal t2g Atomic Orbitals are nonbonding (dxy, dxz, dyz)

6 antibonding orbitals are

formed with the same
symmetries as the bonding
orbitals

The 2 eg* antibonding

orbitals are the lowest
energy antibonding orbitals
available

The d-electrons from the

metal ion will fill in the t2g
and eg* MO’s

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 All octahedral metal complexes will have the exact same MO
diagram, only the number of d-electrons will change
 The 6 bonding MO’s, with lowered energy for their electron pairs is
what holds the metal complex together
 The d-electrons in the t2g and eg* MO’s
 Determine the “Ligand Field”
 Determine the geometry and many characteristics of the metal complex

Ligand Field Stabilization Energy = LFSE

 LFSE = energetic stabilization of the d-electrons due to orbital
splitting (measured in units of Do)

 Essentially equivalent to CFSE, although the theoretical approach is

different

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.

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 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 spin-only magnetic
moment, μs, can be used to determine the number of
unpaired electrons.
μs = [n(n+2)]1/2

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

High Spin vs. Low Spin

3d metals are generally high spin complexes except with

very strong ligands. CN– forms low spin complexes,
especially with M3+ ions.

4d & 5d metals generally have a larger value of ∆O than

for 3d metals. As a result, complexes are typically low
spin.

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 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 σ bonds with the metal. Many ligands can also
form π bonds with the metal. Group theory greatly
simplifies the construction of molecular orbital diagrams.

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

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 z Considering π Bonding
x z
y Consider only the px and pz orbitals
y x
x on each of the ligands to obtain Γπ.
y y x
z z
z y Group orbital approach to π-bonding
x y a) Choose x, y, z axes so that y points
z directly at metal (σ)
x
b) Find the reducible representation of the
12 px and pz orbitals

8C 6C 3C2
Oh E 6C4 i 6S4 8S 3σh 6σd
3 2 (=C42) 6

1
Γπ 0 0 0 –4 0 0 0 0 0
2

Considering π Bonding
8C 3C2
Oh E 6C2 6C4 i 6S4 8S6 3σh 6σd
3 (=C42)
Γπ 12 0 0 0 –4 0 0 0 0 0

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

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

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 Considering π Bonding
Tπ reduces to: T1g + T2g + T1u + T2u

 The T1g and T2u orbitals for the ligands don’t match the
symmetry of any of the metal orbitals.
 T2g set symmetry matches with metal dxy, dyz and dxz
orbitals (T2g) for p-bonding.
 T1u set symmetry matches with metal px, py and pz
orbitals on the metal. But these metal orbitals are already
used to make the σ bonds to the ligands.

Metal have (Eg + T2g + A1g + T1u)

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

Ligand having empty d or π* orbitals serve as a π-acceptor ligand,

and
Ligand with full p or d orbitals and serve as a π-donor ligand.

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 π Bonding

OR

a) Overlap Metal t2g + p orbital; b) Overlap Metal t2g + ligand (d) t2g
c) Overlap Metal t2g + p* orbital

π Donor Ligands (LM)

 All ligands are σ donors. Ligands with filled p or d orbitals
may also serve as πdonor ligands.
 Examples:π 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 MOs.

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 p-donor ligand is a ligand that, before any bonding is conside-
red, has filled orbitals of p symmetry around the M-L axis. The
energies of these full p orbitals are usually close to, but somewhat
lower than, those of the metal d orbitals. We need consider only
the full orbitals when considering the effects of p bonding in the
complex. Such ligands include Cl-, Br- and H2O.The net effect is
that nonbonding metal-ion t2g orbitals become antibonding and
hence are raised closer in energy to the mainly metal antibonding eg
orbital.
It follows that strong p donor ligands decrease Do.

π Donor Ligands (LM)

The effect of p bonding on the ligand-

field splitting parameter.
Ligands that act as p-donors decrease Do.

The bonding orbitals, which are

lower in energy, are primarily filled
with electrons from the ligand, and
the antibonding MOs are primarily
occupied by electrons from the metal.

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 π 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 πdonor ligands.

Example: F– ligand
a) Filled p-orbitals are the only
orbitals capable of p-interactions
1. 1 lone pair used in s-bonding
2. Other lone pairs p-bond
b) The filled p-orbitals are lower in
energy than the metal t2g set
c) Bonding Interaction
1. 3 new bonding MO’s filled by
Fluorine electrons
2. 3 new antibonding MO’s form
t2g* set contain d-electrons
3. Do is decreased (weak field)
d) Ligand to metal (LM) p-
bonding
1. Weak field, p-donors: F, Cl, H2O
2. Favors high spin complexes

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 π Acceptor Ligands (ML)
 Ligands such as CN, N2 and CO have empty π antibonding
orbitals of the proper symmetry and energy to interact with
filled d orbitals on the metal.
 The empty π antibonding orbital on CO can accept
electron density from a filled d orbital on the metal.
CO is a π acceptor ligand.

filled d empty π*
orbital orbital

π Acceptor Ligands (ML)

The metal uses the t2g set of

orbitals (dxy, dyz and dxz) to
engage in πbonding with the
ligand. The π* orbitals on the
ligand are usually higher in
energy than the d orbitals on
the metal.

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 π 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 π* orbitals
on the ligand are usually
higher in energy than the d
orbitals on the metal.
 The interaction causes the
energy of the t2g bonding
orbitals to drop slightly, thus
increasing the size of ∆o.

π Acceptor Ligands (ML)

A p-acceptor ligand is a ligand that has filled p orbitals at lower

energies than metal t2g orbitals, it also has empty p orbitals that are
available for occupation. The p acceptor orbitals are vacant
antibonding orbitals on the ligand, as in CO and N2, and these orbitals
lie above the metal d orbitals in energy. The p-donor character of CO
is very low and in most d-metal carbonyl complexes CO is a net p
acceptor.
Because the p-acceptor orbitals on most ligands are higher energy
than the metal d orbitals. They form MO orbitals in which the
bonding t2g combinations are largely of metal d orbitals character.
The net result is that Do is increased by the p-acceptor interaction.

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 Carbon monoxide (CO)
σ*2p
(sp) 2 π*2p When acting as an electron
pair acceptor, the lowest
2p
2p
unoccupied molecular orbital
E σ*2s
σ2p (LUMO), is significant.
2s
π2p
(sp)1

2s
σ2s
C A.O. CO M.O. O A.O.

CN– Example:
1. HOMO = s-bonding electron
pair donor to metal ion
2. LUMO = p-bonding electron
pair acceptor from metal ion
3. The p* orbitals are higher in
energy than the metal t2g
orbitals having the correct
symmetry to overlap with
4. The energy match is good
enough for overlap to occur
5. p-bonding results

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1. 3 new bonding t2g MO’s receive
the d-electrons
2. 3 new antibonding t2g* MO’s
formed
3. The eg* MO’s from the s-bond
MO treatment are nonbonding
4. Ligands like this increase Δo by
lowering the energy of t2g MO’s
favoring low spin complexes
5. CN– is a strong field ligand
6. Metal to Ligand (ML) or p-
back bonding to p-acceptor
ligand
7. Transfer of electron density away
from M+ stabilizes the complex
over s-bonding only

π donors ligands show

smaller value of ∆o.

π acceptor ligands show

larger value of ∆o.

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 Summary
1. All ligands are σ donors. In general, ligand that engage
solely in σ bonding are in the middle of the
spectrochemical series. Some very strong σ donors,
such as CH3– and H– are found high in the series.
2. Ligands with filled p or d orbitals can also serve as π
donors. This results in a smaller value of ∆o.
3. Ligands with empty p, d or π* orbitals can also serve as
π acceptors. This results in a larger value of ∆o.

I– < Br– < Cl– < F– < H2O < NH3 < PPh3 < CO
π donor < weak π donor <σ only < π acceptor

Summary
The overall order of the spectrochemical series may be interpreted in
broad terms as dominated by p effect, and in general the series can
be interpreted as follows:

-increasing Do 
p Donor < weak p donor < no p effects < p acceptor

Representative ligands that match these classes are

I– < Br– < Cl– < F– < H2O < NH3 < PR3 < CO
p Donor < weak p donor < no p effects < p acceptor

p- donor ligands decrease Do and p -acceptor ligands increase Do; the

spectrochemical series is largely a consequence of the effects of p
bonding when such bonding is feasible.

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