Bonding Theories of

Coordination Chemistry
Dr. Nishantha K. Kalutharage
PhD, Marquette, USA
In the formation of complexes, classify the
transition metal ion and the ligand as a Lewis acid
or base. Explain your answer briefly.

The transition metal ion is the Lewis acid since it

accepts lone pairs of electrons from the ligands in
forming dative covalent bonds.
The ligand is the Lewis base since it donates a lone
pair of electrons to the transition metal ion in
forming dative covalent bonds.
 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.

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Bonding Theories of Coordination Chemistry

Three Major Theories

• Valance Bond Theory (VBT)
• Crystal Field Theory (CFT)
• Modified CFT, known as Ligand Field Theory
• Molecular Orbital Theory (MOT)
 Valance Bond Theory

Basic Principle

A covalent bond forms when the

orbtials of two atoms overlap and
are occupied by a pair of electrons
Linus Carl Pauling
that have the highest probability (1901-1994)
of being located between the Nobel prizes: 1954, 1962
nuclei.
 VBT
• He applied VBTto coordination compounds.
• VBT can account reasonably well for the structure and
magnetic properties of metal complexes.
• The basic principles, which are involved in the VB
treatment of coordination compounds are:
a) Hybridization of valance orbitals of the central metal/
ion
b) Bonding between ligand and the metal ion/atom.
c) Relation between the type of bond and the observed2/25/2019

magnetic behaviour
 Complex geometry can be linked to five main
orbital hybridization processes.

Coordinati Geometry Hybrid Example

on number orbitals

2 Linear sp [Ag(NH3)2]+

4 Tetrahedral sp3 [CoCl4]2-

4 Square planer dsp3 [Ni(CN)4]2-

6 Octahedral d2sp3 or [Cr(H2O)6]3+,

sp3d2 [Co(H2O)6]2+
Two Possible Ways

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 VBT and Magnetism
Tetrahedral complex [CoCl4 ]2−

Gives [CoCl4]2– three unpaired electrons, which makes it

paramagnetic and attracted by magnets.
 Square Planar Geometry

Gives [Ni(CN)4]2– all paired electrons, which makes it

diamagnetic and weakly repelled by magnets.
 Octahedral sp3d2 Geometry
Gives [CoF6]3– four unpaired electrons, which makes it
paramagnetic and is called a high-spin complex.
 Octahedral d2sp3 Geometry
[Fe(CN)6 ]3–

CN– Strong ligand

(Inner orbital complex)
• The difference between sp3d2 and d2sp3
hybrids lies in the principal quantum number
of the d orbital.

• In sp3d2 hybrids, the s, p, and d orbitals

have the same principal quantum number—
High Spin.

• In d2sp3 hybrids, the principal quantum

number of the d orbitals is one less than s
and p orbitals—Low Spin.

• A complex’s magnetic properties determine

which hybrid is being used.
 Magnetic behaviour

M  n(n  2)
Where n is the number of unpaired electrons
 Exercise 1
Discuss the geometry of the compound [Cr(CO)6].

Solution
5 1 0
3d 4s 4p
Ground state Cr
6 0 0
3d 4s 4p
Excited state Cr(0)

Hybridization state

Electrons donated by
2 ligand 'CO'
3
d sp hybridization = octahedral geometry
 Exercise 2
Discuss the geometry of [PtCl4]2- and [NiCl4]2- .

Solution:Geometry of [PtCl4]2-
8 0 0
5d 6s 6p
2+
Ground state Pt
8 0 0
5d 6s 6p
2+
Excited state Pt
Hybridization state

-
Electrons donated by
dsp2 hybrid = square planar. ligand '4Cl- '
Geometry of [NiCl4]2-
8 0 0
3d 4s 4p
2+
Ground state Ni

Hybridization state

-
Electrons donated by
-
ligand '4Cl '
sp3 hybrid = tetrahedral.
 Exercise 3
[Co(NH3)6]3+ is diamagnetic and [CoF6]3- is paramagnetic. Explain
with the help of valence bond theory.

Solution
6 0 0
3d 4s 4p
3+
Ground state Co
6 0 0
3d 4s 4p
3+
Excited state Co
Hybridization state

Electrons donated by
ligand '6NH3'
[CoF6]3-
6 0 0
3d 4s 4p
3+
Ground state Co

4s 4p 4d
Hybridization state

Electrons donated by
ligand '6F- '
 Limitations of VBT
The VB theory, explains the formation, structures and magnetic behaviour of
coordination compounds, it suffers from the following shortcomings:
(i) It involves a number of assumptions.
(ii) It does not give quantitative interpretation of magnetic data.
(iii) It does not explain the colour exhibited by coordination
compounds.
(iv) It does not give a quantitative interpretation of the
thermodynamic or kinetic stabilities of coordination compounds.
(v) It does not make exact predictions regarding the tetrahedral
and square planar structures of 4-coordinate complexes.
(vi) It does not distinguish between weak and strong ligands.
 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.

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 Crystal Field Theory

• Focus: energies of the d orbitals

• Assumptions
• 1. Ligands: negative point charges
• 2. Metal-ligand bonding: entirely ionic
• strong-field (low-spin): large splitting of d orbitals
• weak-field (high-spin): small splitting of d orbitals
 Crystal Field Theory

Bonding model explaining many important

properties of
transition-metal complexes:
 Crystal Field Theory

Central assumption of CFT:

metal-ligand connections are

electrostatic interactions btwn
a central metal ion

and a set of negatively charged

ligands (or ligand dipoles)
arranged around metal ion.
 d-Orbital Splittings
five d orbitals are initially degenerate
(same energy).

When the 6 (-) charges

are distributed uniformly over
surface of a sphere,
d orbitals remain degenerate.
• We assume an octahedral array of negative charges placed around
the metal ion (which is positive).
• The ligand and orbitals lie on the same axes as negative charges.
– Therefore, there is a large, unfavorable interaction between
ligand (-) and these orbitals.
– These orbitals form the degenerate high energy pair of energy
levels.
• The dxy, dyz, and dxz orbitals bisect the negative charges.
– Therefore, there is a smaller repulsion between ligand and metal
for these orbitals.
– These orbitals form the degenerate low energy set of energy
levels.
 d-Orbital Splittings

But!
Their energy will be higher
due to
Ligands will interact with some d orbitals more than others

Depends on relative orientation of orbital and ligand

Ligands point right at lobes

In these orbitals, the ligands are between the lobes
Interact less strongly
 d-Orbital Splittings

If the 6 (-) charges are placed at vertices

of an octahedron,

avg energy of d orbitals

does not change.
 d-Orbital Splittings

But!
It does remove their degeneracy
and the 5 d orbitals split into two groups
 d-Orbital Splittings
The dx2 – y2 and dz2 orbitals (eg orbitals)
point directly at the six (-) charges,

which increase their Energy compared with

a spherical distribution of negative charge.
 The dxy, dxz, & dyz (t2g orbitals)
are all oriented at a 45º angle to the coordinate axes
and point between the 6 (-) charges,
which decreases their Energy
compared with a spherical distribution of charge
Crystal field splitting of the 5 d orbitals by the “crystal field” of 6
ligands

eg orbitals

Orbitals “on axis”: “energy increases”

Crystal field
splitting

t2g orbitals 40

Orbitals “off axis”: “energy decreases”

Ligand field theory considers the effect of different ligand
environments (ligand fields) on the energies of the d-
orbitals.

The energies of the d orbitals in different environments

determines the magnetic and electronic spectral properties
of transition metal complexes.

Ligand field theory combines an electrostatic model of

metal-ligand interactions (crystal field theory) and a
covalent model (molecular orbital theory).
As LP’s on ligands approach along x, y, and z axes.
 d-Orbital Splittings
Difference in E btwn the two sets of d orbitals is
crystal field splitting energy (CFSE) Do.
eg

3/5 Do

Do
2/5 Do
t2g

E(t2g) = -0.4Do x 3 = -1.2Do

E(eg) = +0.6Do x 2 = +1.2Do
 d-Orbital Splittings

Magnitude of the splitting depends on:

Splitting of d orbitals in a crystal field

does not D total energy
of the five d orbitals
 Electronic Structures of Metal Complexes
Using d-orbital energy-level diagram:
electronic structures & some properties of
transition-metal complexes can be predicted.

Start with Ti3+ ion,

(contains a single d electron),
proceed across first row of transition metals
by adding a single e- at a time.
Additional e-’s placed in lowest-E orbital available
while keeping their spins parallel
 For d1-d3 systems,
e-’s successively occupy the 3 degenerate t2g orbitals
with their spins parallel (paramagnetic)
giving one, two, and three unpaired electrons.
 Electronic Structures of Metal Complexes
d4 configuration: two possible choices for 4th e-:
enter one of the empty eg orbitals or
enter one of the singly occupied t2g orbitals
D<P D>P
Spin Pairing Energy (P) is an increase in Energy
(due to electrostatic repulsions)
when an e- is put into an occupied orbital.

If Do is < P,
then lowest-energy arrangement has 4th e-
in an empty eg orbital.
Electronic Structures of Metal Complexes

If Do is > P,

lowest-energy arrangement has 4th e-

in one of the occupied t2g orbitals,
Metal ions with d4, d5, d6, or d7 e- configurations
can be either high spin or low spin,
depending on magnitude of Do

magnitude of Do
Large Do =
Smaller Do =
Only one arrangement of d electrons is possible
for metal ions with d8–d10 e- configurations
 Factors That Affect the Magnitude of Do

magnitude of Do dictates whether

a complex with 4, 5, 6, or 7 d e-’s
is high spin or low spin:
1. Large values of Do yield a low-spin complex
2. Small values of Do  a high-spin complex
 Which affects its:
• Magnetic properties
• Structure
• Reactivity
 Factors That Affect the Magnitude of Do
Nature of the ligands
For a series of chem similar ligands,
magnitude of Do decreases
as size of donor atom increases

because smaller, more localized charges

interact
Factors That Affect the Magnitude of Do
Nature of the ligands
 Nature of the ligands
experimentally observed order of
the crystal field splitting energies
produced by different ligands is called:
the spectrochemical series
 Nature of the ligands

1. Strong-field ligands interact strongly

with d orbitals of metal ions
and give a large Do

2. Weak-field ligands interact

more weakly and give a smaller Do
 The Spectrochemical Series
splitting of d orbitals in crystal field model
not only depends on geometry of the complex

also depends on nature of the metal ion,

charge on this ion,
and the ligands that surround the metal.
 The Spectrochemical Series

When geometry and ligands are held constant,

this splitting decreases in the following order:

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

strong-field ions weak-field ions

Metal ions at one end are called strong-field ions,

because splitting due to crystal field is
unusually strong.
Ions at other end are known as weak-field ions.
 The Spectrochemical Series
When geometry & the metal are held constant,
splitting of d orbitals decreases in the following order:

- OH -
CO CN- > NO2- > NH3 > > H2O > F- Cl- > Br-
NCS- - SCN-

strong-field
weak-field ligands
ligands

Strong Field Ligands:

(strongest) CN−, CO > NO2− > en > NH3
Weak Field Ligands:
H2O > ox > OH− > F− > SCN−, Cl− > Br− > I− (weakest)
 tetrahedral crystal field:
imagine 3 ligands lying at alternating corners of a cube
The dx2-y2 & dz2 orbitals
on metal ion at center of the cube
lie between the ligands,
and dxy, dxz, & dyz orbitals point toward the ligands.
 Tetrahedral Complexes

In tetrahedral complexes, orbitals are inverted.

Again because of orientation of orbitals and ligands

D is always small, always low spin (less ligands)

Square planar complexes are different still
 Tetrahedral Complexes
Splitting of energies of orbitals in tetrahedral
complex, Do, is smaller than in an octahedral
complex for two reasons:

1. d orbitals interact less strongly with ligands

in a tetrahedral arrangement.

2. Only four negative charges rather than six,

which decreases electrostatic interactions
 tetrahedral crystal field:

the splitting observed in a tetrahedral crystal field is

opposite of splitting in octahedral complex.
Splitting of d orbitals in a tetrahedral field

t2

Dt

Dt = 4/9Do

Always weak field (high spin)

 With square planar splittings,
energy level for the x2-y2 orbital is very high
so this is an especially good geometry
for d8 complexes, e.g. Pt(II), Ni(II), Pd(II), Au(III)
 Factors That Affect the Magnitude of Do
Charge on the metal ion
Increasing charge on a metal ion has 2 effects:
1. Radius of metal ion decreases
2. Neg charged ligands are more strongly attracted
to it.

Both factors decrease metal-ligand distance,

which causes (-) charged ligands
to interact more strongly with the d orbitals.

magnitude of Do increases
as charge on metal ion increases
Factors That Affect the Magnitude of Do

Principal quantum # of the metal

For a series of complexes of metals

from same group in periodic table
with same charge and same ligands:

magnitude of Do increases with

increasing quantum #:
 Factors That Affect the Magnitude of Do
Principal quantum # of the metal
Do (3d) << Do (4d) < Do (5d)

Increase in Do w/ increasing principal quantum #

is due to: larger radius of valence orbitals
going down a column.

Repulsive ligand-ligand interactions

are important for smaller metal ions,
which results in shorter M–L distances
and stronger d-orbital-ligand interactions
 Colors of Transition-Metal Complexes
Striking colors exhibited by transition-metal complexes
are caused by the excitation of an e- from
a lower-lying d orbital to
a higher-energy d orbital,
which is called a d-d transition
For a photon to affect
the d-d transition,

its E must be = to the

difference in E btwn
the two d orbitals,

which depends on the

magnitude of Do

which depends on the

structure of the
complex.
The energy of a photon of light is inversely
proportional to its wavelength
E = hc = hu
l
Colors of Transition Metal Complexes

CFT helps explain diff colors observed

for complexes
A transition metal complex
absorbs specific l of light
Color observed is complimentary
to what was absorbed
 Observed color is due to transmitted or reflected light
that is complementary in color to light that is absorbed