Recap of Lecture 1

1. Importance of transition metal complexes 2. Ligands and their denticity

3. Werner theory for transition metal complexes 4. Isomerism

 Crystal Field Theory - Introduction
Energy levels of the orbitals Color Magnetic property
Paramagnetic

Striking property of Fe2+

• Energy levels of 3d and 4s orbitals are transition-metal complexes
very close. is the wide range of colors
• Exchange of energy stabilization led to they exhibit.
stable electronic configuration of half-
filled Cr ([Ar] 3d54s1) and filled shells
Cu ([Ar] 3d104s1). Geometry?
• On ionization, 4s electrons are lost first ML4 diamagnetic
and hence ionized complex will stabilize Stability?
the 3d significantly than the 4s orbital.
 Crystal Field Theory - Introduction
Limitations of Valence Bond Theory:

• It fails to provide an explanation for the color exhibited by the

coordination complexes.
• Quantitative interpretation of magnetic data is not given.
• It cannot exactly predict the geometry of the complex having coordination
number four (SP or Td?)
• Weak and strong ligands or high-spin and low-spin complexes cannot be
distinguished.
• The thermodynamic and kinetic stabilities of complexes are not
quantitatively interpreted.
 Crystal Field Theory
• Crystal-field theory, developed by Hans Bethe and John Van Vleck in the 1930s,
assumes that ligands behave as point negative charges, and that the metal-ligand
interaction occurs on several levels.
• The theory was initially used to explain the crystalline material and hence named as
crystal field theory.
• Overall, a complex will be stabilized relative to the free ion, due to the attraction between
the negatively charged ligands and the positively charged metal ion.

• The ligands are considered as point charges.

• The interaction between the metal ion and the ligand is presumed to be electrostatic
(ionic) in nature. In ideal CFT, no covalent interaction between the metal and ligands is
considered.
• Electrostatic perturbation of the metal electron (e.g., d-orbital electron) by the ligands.
• Effect on the energy and degeneracy of the metal orbitals.
http://wwwchem.uwimona.edu.jm/courses/CFT_Orbs.html
 What do d Orbitals Look Like?

The phase of the wave function for the different lobes is

indicated by color: orange for positive and blue for negative.
http://wwwchem.uwimona.edu.jm/courses/CFT_Orbs.html
What do d Orbitals Look Like?

http://wwwchem.uwimona.edu.jm/courses/CFT_Orbs.html
d Orbitals in Octahedral Field
• We assume that the ligand negative
charges are concentrated at six points
representing six octahedrally arranged
ligands, two on the x-axis and two on
the y-axis and two on the z-axis and
approaching the metal through the
axis.
• The orbitals that are oriented along
the axis will be repelled more by the
ligands and hence will be higher than
that of the orbitals that are oriented in
between the axis and will be placed
below the average of the orbitals in the
complex.
CFT CFT
in an in
Octahedral Field:Field
Octahedral Summery

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 CFT in Octahedral Field
• The energy separation between the two levels is
denoted by Δo or 10 Dq.
• The higher energy set of orbitals (dz2 and dx2-y2) are ddxx22-y-y22,,ddzz22
labeled as eg and the lower energy set is labeled as t2g. 10Dq

• To maintain the average energy, the eg orbitals need

to be destabilized by 0.6 Δo (6 Dq) and the t2g orbitals
to be stabilized to the extent of 0.4 Δo (4 Dq)
• t denotes a triply degenerate orbital
• e denotes a doubly degenerate orbital. dxy, dxz, dyz

• The symbol g and u refer to the behavior of an orbital under operation of inversion (applicable
only to complexes that possesses a center of symmetry. g = gerade (symmetric); u = ungerade
(anti-symmetric)
• p-orbitals: signs of the lobe changes on inversion in Oh field; hence they are ungerade.
• There is a center of inversion in s-orbital and hence it is gerade.
 CFT in Tetrahedral Field

t2 orbitals e orbitals
• No orbitals directly pointing towards the
ligands.
• The e orbitals point between the two
ligands present at the opposite corners
t2 of the cube and hence it is less affected
Spherical than the t2 orbitals.
field
e • The t2 orbitals lie half an edge of the
cube from ligand and point more directly
towards ligands and hence more
https://www.dlt.ncssm.edu/tiger/chem8.htm destabilized than e.
Comparison of Octahedral and Tetrahedral Field
• The splitting of the energies of the orbitals
in a tetrahedral complex (Δt) is much
smaller than that for an octahedral complex
(Δo), however, for two reasons: OCTAHEDRON
• The d orbitals interact less strongly with the
ligands in a tetrahedral arrangement.
TETRAHEDRON
• There are only four negatively-charged OCTAHEDRON
regions rather than six, which decreases the
electrostatic interactions by one-third if all 5

other factors are equal.

• The crystal field splitting in the tetrahedral

field is intrinsically smaller than in the
octahedral field. For most purposes, the
relationship may be represented as

Δt = 4/9 Δo
 Determination of △
Determination of Δ
Crystal filed splitting parameter (Δ) is measured by electronic absorption spectroscopy.
Determination of Δ
Ground State Excited State

[Ti(H2O)6]3+

[Ti(H 3+
[Ti 2O)
III(H 6] ]3+
O)
2 6
Determination of Δ
Δ is Relatable to Colour
q Complementary colour wheel.

Absorb Orange See Blue

The maximum absorption peak of [TiIII(H2O)6]3+

Absorb Red See Green

appears at 493 nm (Δo = 20,300 cm-1 = 243 kJ/mol).

The value can be calculated using E = hν = hc/λ
equation.

3+ 1
 Factors that Influence the △
1. Oxidation state of the metal complex
[CoII(NH3)6]2+ Δ = 10,200 cm-1
[CoIII(NH3)6]3+ Δ = 22,870 cm-1
[FeII(CN)6]4- Δ = 32,200 cm-1
[FeIII(CN)6]3- Δ = 35,000 cm-1 [VII(H2O)6]2+ [VIII(H2O)6]3+

Higher ionic charge on the metal ion, pulls the ligands closer towards it and
higher electrostatic repulsion results in larger splitting of d-orbitals

2. Coordination number / Geometry of the complex

[CoII(NH3)6]2+ Δ = 10,200 cm-1
[CoII(NH3)4]2+ Δ = 5,900 cm-1

Tetrahedral complexes ML4 have smaller Δ than octahedral ones (ML6)

 Factors that Influence the △
3. △ value directly proportional to the size of the metal in a group
The splitting of d orbitals in the crystal field model not only depends on the geometry of the complex, it also
depends on the nature of the metal ion, the charge on this ion, and the ligands that surround the metal.
When the geometry and the ligands are held constant, this splitting decreases in the following order.

Pt4+ > Ir3+ > Rh3+ > Co3+ > Cr3+ > Fe3+ > Fe2+ > Co2+ > Ni2+ > Mn2+

• The effective nuclear charge increases in the d-block elements when we move down the group because 4d
series overtakes the effect of increase in nuclear charge.
• The higher the nuclear charge the stronger interaction between the metal nucleus and the ligands.

[MIII(NH3)6]3+
Going Co
down the Rh
[M] [CoIII(NH3)6]3+ [RhIII(NH3)6]3+ [IrIII(NH3)6]3+
group size
increases Ir Δ 22,870 cm-1 34,100 cm-1 41,200 cm-1
 Factors that influence the △
4. Nature of ligands (weak-field vs strong-field ligand)

Effect of Ligands onEffect

the Magnitude of the
of Ligands on Δ Magnitude of Δ
of Ligands on the Magnitude of Δ
q Example nickel complexes q Example nickel complexes
omplexes

[NiII(H2O)6]2+ [NiII(NH3)6]2+ [NiII(en)2]2+ [FeIII(H2O)6]3+ [FeIII(CN)6]3+

q Example chromium complexes
m complexes
q Example chromium complexes

Stronger the ligand, higher the Δ value

 Factors that Influence the △
1. Oxidation state of the metal complex
Higher ionic charge on the metal ion, pulls the ligands closer towards it and
higher electrostatic repulsion results in larger splitting of d-orbitals.

2. Coordination number / Geometry of the complex

Tetrahedral complexes ML4 have smaller Δ than octahedral ones (ML6).

3. △ value directly proportional to the size of the metal in a group

Higher the effective nuclear charge and size of the central metal larger the d-
orbitals splitting Large Δ value.
4. Nature of ligands (weak-field vs strong-field ligand)
Stronger the ligand, higher the Δ value.
 Spectrochemical Series
• The spectrochemical series ranks ligands according to the ability to cause crystal field splitting.
• Ligands that produce a large splitting are called strong field ligands, and those that produce a
small splitting are called weak field ligands.

I- < Br- < Cl- < F-, OH- < H2O < NCS- < NH3 < en < CO, CN-

Weak field ligand Strong field ligand

Analysis of Spectrochemical Series through CFT
• All aspects of spectrochemical series cannot be explained by the basic sets of Crystal Field
Theory.
• How do you rationalize the strength of anionic ligands weaker than the neutral ligands?
Anionic ligands are expected to interact electrostatically more strongly than neutral ligands.
However, many anionic ligands (Br–, Cl–, F– etc.) are relatively weak than neutral CO, Phen etc.
e.g., H2O vs OH- ; The former is a stronger ligand than the latter.
• Orbital interactions need to be invoked to rationalize the order of ligands. Thus, covalency is
incorporated into CFT resulting in the Ligand Field Theory.

• To understand the important concept pertaining to the bonding in coordination compounds,

Ligand Field Theory can be used as tool.

• I– < Br–< Cl–< F– (Ligand Field strength)

Analysis of Spectrochemical Series through CFT
Explanation of Spectrochemical Series using CFT
I– < Br–< Cl–< F– (Ligand Field strength)
I- Br- Cl- F- (Ligand Field strength) : Fluoride ion can
The fluoride ion being
approach muchmuchcloser
smaller.to
Hence,
theaccording
metal ionto CFT, it can approach
thereby closer
increase theto
the metal ion thereby
electronic increasing
repulsion the electronic
which leads torepulsion
higher leading
Δ. to higher Δ.
 Analysis of Spectrochemical
Observation: F OH Series through
O H O (Ligand Field strength) CFT
- - 2-
2

q ligand
• To understand the difference in the Ligands which have filled
strength, let’sp look
orbitalsatmay
theactbonding
as donors by intera
modes
suitable metal orbitals.
between the ligand and the metal
Interaction between dxy of metal and py of halide:
• All ligandsSeries
ectrochemical are “σ donors”. Other than the σ donation, someReducesligands (NOTonall)
positive charge metalcan have
Reduces Δ
additional orbitals that can interact with
Field strength)
other orbitals
Analysis on the metal. Ligand
of the Spectrochemical Field Theory
Series
at the(LFT)
bondingand
modesMolecular
between the Orbital Theory (MOT)- can- properly
Observation: F 2-
OH O
explain this phenomenon.
H2O (Ligand Field strength)
er simplified diagrams for clarity.
• F–, OH–, O2– can rehybridize and donate
q Ligands a pair
which of electrons
have filled p orbitals mayfrom
act as their
donorsfilled p-orbitals
by interacting with to
having a hybrid orbital or a p orbital
symmetrically suitable d-orbitals on
bonds. themetal
suitable metal to form a π-bond.
orbitals.
Interaction between dxy of metal and py of halide:
the ligand to the metal.
Reduces positive charge on2–
metal
FReduces
–< OH
Δ
–< O H2O
Interaction
between qdxyWater
of acts only as a sigma-donor ligand.
metal and py of
halide Reduces
positive charge on
metal Reduces Δ
π-bond
q Water acts only as a sigma-donor ligand. σ-bond
 Analysis of Spectrochemical Series through CFT
St ruct ure and Bonding
M etPPhal, CN
Carbonyl Underst ood
and CO are strong Field Ligands!
–
w it h M OT
3
PPh3
CN– and CO

• Donates its sigma (nonbonding) electrons to the

metal, while accepting electron density from the
metal through overlap of a metal t2g orbital and
a ligand π* orbital, while latter is called back-
bonding.
• Such type of ligand that donates σ-electron
Although, all the ligands are σ donors;
density to the metal and accepts π-electron
in general: π donor < weak π donor <
density to the ligand from the metal is called σ-
donor and a π-acceptor σ only < π acceptor
 Rundown of Ligand Bonding Mode in
Coordination Compounds
• In general, all ligands are σ donors. Ligands that engage solely in σ bonding are in the
middle of the spectrochemical series.
• Ligands with filled p or d orbitals can also serve as π donors. This results in a smaller
value of ∆o.
• 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-, OH- < H2O < NCS- < NH3 < en < CO, CN-

π donor < weak π donor < σ only < π acceptor

Weak field ligand Strong field ligand
 Pairing Energy
• Pairing energy (P) is needed in order to force an
electron to fill an orbital that is already occupied with
ddxx22-y-y22,,dz2 an electron. The electrons can also fill higher energy
dz2 orbitals and avoid the pairing energy.
• The pairing energy, P, depends only on the metal not
on the ligands. It consist of two factors.

1. Electrostatic Repulsion: Coulombic repulsion energy

dxy, dxz, dyz
caused by having two electrons in same orbital.
d4 system Destabilizing energy contribution of Pc for each
doubly occupied orbital.
2. Loss of exchange energy; parallel spin ( ) are forced
to become antiparallel ( ): exchange energy is the
driving force of Hund’s rule of maximum spin
multiplicity. With pairing of electrons, the number of
Low Spin High Spin electron with a particular spin is decreased. This will
lead to the loss of exchange energy. Contribution of Pe
P = Sum of all Pc and Pe interactions for each pair having same spin and same energy.
 High Spin vs Low Spin Complexes
A complex will be high spin or low spin is determined by the Crystal filed splitting parameter
(Δ) and Pairing Energy (P).

For low spin (P < Δ): the energy cost of

placing an electron into an already singly
occupied orbital must be less than the cost of
placing the additional electron into an eg
orbital at an energy cost of Δ.
For high spin (P > Δ): the energy required to
pair two electrons is greater than the energy
cost of placing an electron in an eg, Δ, high
P < Δo P > Δo spin splitting occurs.
 Spin-Cross Over Systems
What happens when Δo is close to P?
When Δo ~ P , interconversion between high spin and low spin states is a possibility.

Temperature or light can assist such interconversion Spin-Cross Over (SCO)

 Some Observations

• 4d & 5d metals generally have a larger value of ∆o than for 3d metals. As a result,
complexes are typically low spin.

• For 3d metals, tetrahedral splitting is rarely large enough to result in pairing of the
electrons. As a result, low-spin tetrahedral complexes are not common.

• High and low spin states occur only for 3d metal complexes with between 4 and 7
d-electrons. Complexes with 1 to 3 d-electrons can accommodate all electrons in
individual orbitals in the t2g set.
 Crystal Field Stabilization Energy (CFSE)
Crystal Field Stabilization Energy (CFSE)
• CFSE is the additional stability
CFSE is the which
additional results
stability from
which placing
results fromaplacing
transition metal ion
a transition in the
metal
crystal field generated
ion in theby a setfield
crystal of ligands through
generated the
by a set ofsplitting of the the
ligands through d-orbitals.
splitting of
the d-orbitals.
CFSE = ΔE = Eligand
CFSE = ΔEfield= −EEligand
isotropic − Eisotropic field
fieldfield
• In this calculation, additional
In this pairing
calculation, compared
additional to the pre-splitting
pairing compare condition
to the pre-splitting should be
condition
included. should be included.
CSFE will depend on multiple factors including:
• CSFE will depend on multiple factors including:
Geometry
✓ Geometry
Number of d-electrons
✓ Number of d-electrons
Spin Pairing Energy
✓ Spin Pairing
Ligand Energy
character
✓ Ligand character
• For an octahedral
Forcomplex, an electron
an octahedral in t2g subset
complex, will contribute
an electron in t2g −2/5 Δo whereas
subset will an
electron in the higher energy
contributes eg subset
−2/5 contributes
Δo whereas to a destabilization
an electron of +3/5 eΔo.
in the higher energy g
subset contributes to a destabilization of +3/5 Δo .
 Worked Examples for d7 HS and LS Systems
High-spin d7 octahedral complex
Eisotropic field = 2P
Eligand field = (5 × −2/5Δo) + (2 × 3/5Δo) + 2P
= −4/5 Δo + 2P

CFSE = (−4/5 Δo + 2P) − 2P = −4/5 Δo

Isotropic Field Ligand Field

Low-spin d7 octahedral complex

Eisotropic field = 2P
Eligand field = (6 × −2/5Δo) + (1 × 3/5Δo) + 3P
= −9/5Δo + 3P

CFSE = (−9/5 Δo + 3P) − 2P = −9/5 Δo + P

Isotropic Field Ligand Field
 CFSE for Oh Complexes
High Spin Low Spin
d1 t2g1eg0 -2/5 Δo t2g1eg0 -2/5 Δo
d2 t2g2eg0 -4/5 Δo t2g2eg0 -4/5 Δo
d3 t2g3eg0 -6/5 Δo t2g3eg0 -6/5 Δo
d4 t2g3eg1 -3/5 Δo t2g4eg0 -8/5 Δo + P
d5 t2g3eg2 0 Δo t2g5eg0 -10/5 Δo + 2P
d6 t2g4eg2 -2/5 Δo t2g6eg0 -12/5 Δo + 2P
d7 t2g5eg2 -4/5 Δo t2g6eg1 -9/5 Δo + P
d8 t2g6eg2 -6/5 Δo t2g6eg2 -6/5 Δo
d9 t2g6eg3 -3/5 Δo t2g6eg3 -3/5 Δo
d10 t2g6eg4 0 Δo t2g6eg4 0 Δo
 CFSE for Td Complexes
Configuration CFSE
Tetrahedral d1 e1t20 -0.6 Δt
splitting is d2 e2t20 -1.2 Δt
seldom large
d3 e2t21 -0.8 Δt
enough to result
in pairing of the d4 e2t22 -0.4 Δt
electrons. As a d5 e2t23 0 Δt
result, low-spin d6 e3t23 -0.6 Δt
tetrahedral d7 e4t23 -1.2 Δt
complexes are
d8 e4t24 -0.8 Δt
not common.
d9 e4t25 -0.4 Δt
d10 e4t26 0 Δt
 Octahedral vs Tetrahedral Complexes
• Assuming high spin configurations. The units are Δo, and Δt = 4/9 Δo. Ignore their
signs since we're looking for the difference between them.
Octahedral Tetrahedral Difference
d0, d5, d10 0 0 0
d1, d6 0.4 0.27 0.13
d2, d7 0.8 0.53 0.27
d3, d8 1.2 0.36 0.84
d4, d9 0.6 0.18 0.42

The ordering of favorability of octahedral over tetrahedral is:

d3, d8 > d4, d9> d2, d7 > d1, d6 > d0, d5, d10
If large or highly charged ligands are present, to avoid ligand-ligand repulsion
they may prefer a lower coordination number (4 instead of 6)
 ForOctahedral vs
d1 there's only a small Tetrahedral
gap between the octComplexes
and tet lines, whereas at
d3 and d8 there's a big gap.
• In in most cases, CFSE favors octahedral over tetrahedral geometry, but the degree of
However,
favorability variesfor d0the
with , d5electronic and d10, there is no CFSE difference between
high spinconfiguration.
octahedral and tetrahedral.
• For d1 there's only a small gap between the Oh and
If whereas
Th lines, large orat highly
d3 and d8charged ligands
there's a big gap. are
present, to avoid ligand-ligand repulsion
they may prefer a lower coordination
• However, for d 0, d5 high spin and d10, there is no CFSE
number (4 instead of 6)
difference between octahedral and tetrahedral.

• If large or highly charged ligands are present, to avoid ligand-ligand repulsion they may
prefer a lower coordination number 4 instead of 6.
27
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 Square Planar Complexes
• Let’s assume that we remove the two
axial ligands along the ± Z axes from
Tetragonal distortion
the octahedral complex. Due to
removal of ligands at the axial
position, the electrostatic interaction
get decreased and hence d-orbitals
with z-component will fall in energy.
• The dz2 orbital points directly at the
two ligands being removed, its
energy will decrease much more
rapidly than the degenerate energies
of the dxz and dyz.
• Energy of dx2−y2 and the dxy orbitals
will increase. As dx2−y2 orbital points
directly at the four in-plane ligands,
its energy increases to a greater
extent than the energy of the dxy
orbital.