Bonding in coordination compounds

• Introduction….
Nobel prize 1913
• Alfred Werner - 1893
• VBT
• Crystal Field Theory (CFT)
• Modified CFT, known as
Ligand Field Theory
• MOT
[Fe(H2O)6]3+ [Ni(H2O)6]2+ [Zn(H2O)6]2+
[Co(H2O)6]2+ [Cu(H2O)6]2+
 Gemstone owe their color from
trace transition-metal ions
• Corundum mineral, Al2O3: Colorless
• Cr g Al : Ruby
• Mn g Al: Amethyst
• Fe g Al: Topaz
• Ti &Co g Al: Sapphire

• Beryl mineral, Be3 Al 2Si6O18: Colorless

• Cr g Al : Emerald
• Fe g Al : Aquamarine
 Coordination Chemistry

Transition elements: partly filed d or f shells

Which elements should be considered as transition elements?

Why do we consider the 1st row separately from others?
 What is a transition metal?
• Transition metals [TM’s] have characteristic
properties
– e.g. coloured compounds, variable oxidation states
• These are due to presence of an inner incomplete d
sub-shell
• Electrons from both inner d sub-shell and outer s
sub-shell can be involved in compound formation
 The d block:
• The d block consists of three horizontal series in
periods 4, 5 & 6
– 10 elements in each series
– Chemistry is “different” from other elements
– Special electronic configurations important
• Differences within a group in the d block are less sharp
than in s & p block
• Similarities across a period are greater
 What is a transition metal?

• For this reason, a transition metal is defined

as being an element which forms at least
one ion with a partially filled sub-shell of d
electrons.
– In period 4 only Ti-Cu are TM’s!
– Note that when d block elements form ions the
s electrons are lost first
 TM complex: Variable valence

Sc +3

Ti +1 +2 +3 +4
V +1 +2 +3 +4 +5
Cr +1 +2 +3 +4 +5 +6 Cu is the only element
Mn +1 +2 +3 +4 +5 +6 +7 which affords CuI
Fe +1 +2 +3 +4 +5 +6 compounds without π-
Co +1 +2 +3 +4 +5
acceptor ligands
becoz it does not have greater affinity for electrons rather it
wants to donate
Ni +1 +2 +3 +4

Cu +1 +2 +3

Zn +2
 Complexes: Have metal ion (can be zero oxidation state)
bonded to number of ligands.
Complex contains central metal ion bonded to one
or more molecules or anions
Lewis acid = metal = center of coordination

Transition metals can act as Lewis acid

Lewis base = ligand = molecules/ions covalently
bonded to metal in complex

The term ligand (ligare [Latin], to bind) was first used by

Alfred Stock in 1916 in relation to silicon chemistry. The first use
of the term in a British journal was by H. Irving and R.J.P. Williams
in Nature, 1948, 162, 746.

For a fascinating review on 'ligand' in chemistry - Polyhedron, 2, 1983, 1-7.

Ligand: Lewis base – contain at least one nonbonding pair of
electrons
Ni2+(aq) + 6NH3(aq) → Ni(NH3)62+(aq)
Lewis acid Lewis base Complex ion

¿Coordination compound
©Compound that contains 1 or more complexes
©Example
ô[Co(NH3)6]Cl3

ô[Cu(NH3)4][PtCl4]

ô[Pt(NH3)2Cl2]
How & Why?
 Valance Bond Theory

Basic Principle

A covalent bond forms when the orbtials of two

atoms overlap and are occupied by a pair of
electrons that have the highest probability of
being located between the nuclei.
Linus Carl Pauling
(1901-1994)
Nobel prizes: 1954, 1962
 Valance Bond Model
Ligand = Lewis base
Metal = Lewis acid
s, p and d orbitals give hybrid orbitals with specific geometries
Number and type of M-L hybrid orbitals determines geometry of the complex

Octahedral Complex
e.g. [Cr(NH3)6]3+
Tetrahedral e.g. [Zn(OH)4]2- Square Planar e.g. [Ni(CN)4]2-

Limitations of VB theory
Cannot account for colour of complexes
May predict magnetism wrongly
Cannot account for spectrochemical series
Crystal Field Theory
400 500 600 800

•The
relationship
between colors
and complex
metal ions
 Crystal Field Model
A purely ionic model for transition metal complexes.
Ligands are considered as point charge.
Predicts the pattern of splitting of d-orbitals.
Used to rationalize spectroscopic and magnetic
properties.
d-orbitals: look attentively along the axis
Linear combination of
dz2-dx2 and dz2-dy2

d2z2-x2-y2
Octahedral Field
• 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 x -y d z2
2 2

Δo
or
10 Dq

dxy dyz dxz

 d x -y d z2
2 2

+ 0.6
Δo
or
+ 6 Dq

- 0.4 Δo
or
- 4 Dq

dxy dyz dxz

In Octahedral Field
dyz

dz2

dxz

dx2-
y2 dxy
In Tetrahedral Field
Tetragonal Distortion
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.
 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 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.
 Electronic configuration and J-T 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)
# e- 1 2 3 4 5 6 7 8 9 10
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.
d9 system
d7 system (low spin)
d4 system (high spin)
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 4-coordinate
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 four-coordinate
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).
 Magnitude of Δ

Oxidation state of the metal ion proportional to os

[Ru(H2O)6]2+ 19800 cm-1
[Ru(H2O)6]3+ 28600 cm-1

Number of ligands and geometry

Δt< Δo Δt= 4/9Δo

Nature of the ligand

I-<S2-<SCN-<Cl-<NO3-<N3-<F-<OH-<C2O42-<H2O<…..CN-<CO
 Crystal Field Splitting Energy (CFSE)
• In Octahedral field, configuration is: t2gx egy
• Net energy of the configuration relative to the
average energy of the orbitals is:
= (-0.4x + 0.6y)ΔO
ΔO = 10 Dq
BEYOND d3
• In weak field: ΔO < P, => t2g3eg1
• In strong field ΔO > P, => t2g4
• P - paring energy
Hydration Enthalpy of M2+ ions (H2O is weak field ligand, the
complexes are high spin).

M2+(g) + 6 H2O(l) = [M(O2H)6]2+(aq)

Plotting the enthalpy across the first transition series

Ground-state Electronic Configuration,
Magnetic Properties and Colour
When the 4th electron is assigned it will either go into the higher
energy eg orbital at an energy cost of Δo or be paired at an energy
cost of P, the pairing energy.

d4

Strong field = Weak field =

Low spin High spin
(2 unpaired) (4 unpaired)

P < Δo P > Δo
Coulombic repulsion energy and exchange energy
Ground-state Electronic Configuration,
Magnetic Properties and Colour
[Mn(H2O)6]3+
Weak Field Complex
the total spin is 4 × ½ = 2
High Spin Complex

[Mn(CN)6]3-
Strong field Complex
total spin is 2 × ½ = 1
Low Spin Complex
 Placing electrons in d orbitals

d5 d6 d7

1 u.e. 5 u.e. 0 u.e. 4 u.e. 1 u.e. 3 u.e.

d8 d9 d10

2 u.e. 2 u.e. 1 u.e. 1 u.e. 0 u.e. 0 u.e.

What is the CFSE of [Fe(CN)6]3-?
CN- = s.f.l.
C.N. = 6 ∴ Oh Fe(III) ∴ d5 h.s. l.s.
CN 3-
eg eg
CN
NC + 0.6 Δoct
Fe
NC CN
- 0.4 Δoct
CN t2g
t2g

CFSE = 5 x - 0.4 Δoct + 2P = - 2.0 Δoct + 2P

If the CFSE of [Co(H2O)6]2+ is -0.8 Δoct, what spin state is it in?

C.N. = 6 ∴ Oh Co(II) ∴ d7 h.s. l.s.

OH2 2+ eg
eg
OH2 + 0.6 Δoct
H2O
Co
H2O OH2 - 0.4 Δoct
t2g t2g
OH2

CFSE = (5 x - 0.4 Δoct) CFSE = (6 x - 0.4 Δoct)

+ (2 x 0.6 Δoct) +2P = - 0.8 Δoct+2P + (0.6 Δoct) + 3P= - 1.8 Δoct + P
 The origin of the color of the transition
metal compounds
E2

ΔE hν

E1

ΔE = E2 – E1 = hν
Ligands influence ΔO, therefore the colour
The colour can change depending on a number of factors
e.g.
1. Metal charge
2. Ligand strength
The optical absorption spectrum of [Ti(H2O)6]3+

Assigned transition:
eg t2g
This corresponds to
the energy gap
ΔO = 243 kJ mol-1

490 nm
 IMPOR
TANT

absorbed observed
color color
• Spectrochemical Series: An order of ligand
field strength based on experiment:
Weak Field I- < Br-< S2-< SCN-< Cl-<
NO3-< F- < C2O42-< H2O< NCS-<
CH3CN< NH3< en < bipy< phen<
NO2-< PPh3< CN-< CO Strong Field

H2N NH2
N
N N N
Ethylenediamine (en)
2,2'-bipyridine (bipy) 1.10 - penanthroline (phen)
Spectrochemical Series
Or more simply :
X<O<N<C
 [CrF6]3- [Cr(H2O)6]3+ [Cr(NH3)6]3+ [Cr(CN)6]3-

As Cr3+ goes from being attached to a weak field

ligand to a strong field ligand, Δ increases and the
color of the complex changes from green to yellow.
[Fe(H2O)6]3+ [Ni(H2O)6]2+ [Zn(H2O)6]2+
[Co(H2O)6]2+ [Cu(H2O)6]2+
Intensity of color?
Selection rule
 n = no. of unpaired electrons
µ = {n(n+2)}1/2 µB
µ = 2{S(S+1)}1/2
Ion n S µ/µB Experimental
Calculate
d
Ti3+ 1 1/2 1.73 1.7 – 1.8
V3+ 2 1 2.83 2.7 – 2.9
3+
Cr 3 3/2 3.87 3.8
Mn3+ 4 2 4.90 4.8 – 4.9
Fe3+ 5 5/2 5.92 5.3

Similar Calculation can be done

for Low-spin Complex
• The magnetic moment µ of a complex with total
spin quantum number S is:
• µ = 2{S(S+1)}1/2 µB (µB is the Bohr magneton)
• µB = eh/4πme = 9.274 ×10-24 J T-1
• Since each unpaired electron has a spin ½,
• S = (½)n, where n = no. of unpaired electrons
• µ = {n(n+2)}1/2 µB
• In d4, d5, d6, and d7 octahedral complexes,
magnetic measurements can very easily predict
weak versus strong field.
• Tetrahedral complexes - only high spin
complexes result, for Δt << ΔO.
Determination Magnetic Properties
Gouy balance to
measure the magnetic
susceptibilities
 Limitations of CFT
Considers Ligand as Point charge/dipole only
Does not take into account of the overlap of ligand and
metal orbitals

Consequence
e.g. Fails to explain why CO is stronger ligand than CN- in
complexes having metal in low oxidation state
 Metals in Low Oxidation States

• In low oxidation states, the electron density

on the metal ion is very high.
• To stabilize low oxidation states, we require
ligands, which can simultaneously bind the
metal center and also withdraw electron
density from it.

• Very Interesting: We shall discuss about this

in Organometallic/Catalysis topic
Note: You need to know CHELATE EFFECT

•to understand chemistry of transition metal

complexes with multidentate ligands

•to understand mode of action of transition

m e t a l c o m p l exe s i n b i o l o g y / r e a l l i fe
applications

CHELATE EFFECT will be

discussed in Tutorial Classes