Inorganic Chemistry

Books to Refer:
1. Inorganic Chemistry by Shriver & Atkins
2. Inorganic Chemistry by James E. Huheey
3. WILEY Engineering Chemistry – 2nd Ed. 2013
4. Solid State Chemistry: An introduction, 4th Ed.,
CRC Press.; Moore and Smart.
 Inorganic Syllabus
Chapter-1: Bonding and Coordination Chemistry
Chapter-2: Organometallics and Catalysis
Chapter-3: Redox chemistry
Chapter-4: Materials Chemistry

•  Bonding and Coordination Chemistry: Bonding in homo- (Li2 to N2 O2 and F2) and
heterodinuclear (only CO). CFT and application of CFT. From Laboratory to Living Systems.
Spectroscopic, magnetic, functional properties of new age coordination compounds, and
Hemoglobin. (5 lectures)

•  Organometallics and Catalysis: Metal carbonyls. Oxidative addition and reductive

elimination, insertion and elimination reactions. Hydrogenation (Wilkinson’s catalyst),
Carbonylation (Monsanto Process)
(3 lectures)

•  Redox chemistry: Diagrammatic representation and use of Latimer and Frost diagram.
Applications of redox chemistry in energy storage (primary and secondary batteries).
(3 lectures)
•  Materials Chemistry: Metal oxides, spinel, superconductor, and boron nitride.
(1-2 lectures)
 Important Instruction
•  Must attend all the Regular and Tutorial classes

Mode of Evaluation
•  3 (Three) Assignments: Detail instruction will be sent

•  One Online Test for Inorganic (through moodle platform)

 Tutorial Classes
• Online platform: Googlemeet
• Separate link will be shared by TA

What to do in Tutorial Classes?

Doubt clearing/additional discussion/Question-Answer

Section Day and Time TA’s name TA’s email id

15 (A+B)

15 (C+D)

16 (A+B)

16 (C+D)
What is Inorganic Chemistry? Why to read? Role in real life?
 Chemical Bonding
•  Two existing theories,
•  Molecular Orbital Theory (MOT)
•  Valence Bond Theory (VBT)
Molecular Orbital Theory
•  MOT starts with the idea that the quantum
mechanical principles applied to atoms
may be applied equally well to the
molecules.
 MOT: We can write the following principles
☛  Describe Each electron in a molecule by a
certain wave function Ψ - Molecular Orbital
(MO).
☛  Each Ψ is defined by certain quantum numbers,
which govern its energy and its shape.
☛  Each Ψ is associated with a definite energy
value.
☛  Each electron has a spin, ± ½ and labeled by its
spin quantum number ms.
☛  When building the molecule- Aufbau Principle
(Building Principle) - Pauli Exclusion Principle.
 Simplest possible molecule:
H2+ : 2 nuclei and 1 electron.
•  Let the two nuclei be labeled as A and B &
wave functions as ΨA & ΨB.
•  Since the complete MO has characteristics
separately possessed by ΨA and ΨB,
•  Ψ = CAΨA + CBΨB
•  or Ψ = N(ΨA +λ ΨB)
•  λ = CB/CA, and N - normalization constant
This method is known as Linear Combination
of Atomic Orbitals or LCAO

•  ΨA and ΨB are same atomic orbitals except

for their different origin.
•  By symmetry ΨA and ΨB must appear with
equal weight and we can therefore write
•  λ2 = 1, or λ = ±1
•  Therefore, the two allowed MO’s are
•  Ψ = ΨA± ΨB
 For ΨA+ ΨB
we can now calculate the energy

•  From Variation Theorem we can write the

energy function as

•  E = <ΨA+ΨB ⎢H ⎢ΨA+ΨB>/<ΨA+ΨB ⎢ΨA+ΨB>

 Looking at the numerator:
E = <ΨA+ΨB ⎢H ⎢ΨA+ΨB>/<ΨA+ΨB ⎢ΨA+ΨB>

•  <ΨA+ΨB ⎢H ⎢ ΨA+ΨB> = <ΨA ⎢H ⎢ΨA> +

•  <ΨB ⎢H ⎢ΨB> +

•  <ΨA ⎢H ⎢ΨB> +

•  <ΨB ⎢H ⎢ΨA>

•  = <ΨA ⎢H ⎢ ΨA> + <ΨB ⎢H ⎢ΨB> +2<ΨA⎢H ⎢ΨB>

 = <ΨA ⎢H ⎢ ΨA> + <ΨB ⎢H ⎢ΨB> + 2<ΨA⎢H ⎢ΨB>

ground state energy of a hydrogen

atom. let us call this as EA

<ΨA ⎢H ⎢ ΨB> = <ΨB ⎢H ⎢ΨA> = β

β = resonance integral

∴ Numerator = 2EA + 2 β
 Looking at the denominator:
E = <ΨA+ΨB ⎢H ⎢ΨA+ΨB>/<ΨA+ΨB ⎢ΨA+ΨB>

•  <ΨA+ΨB ⎢ΨA+ΨB> = <ΨA ⎢ΨA> +

•  <ΨB ⎢ΨB> +
•  <ΨA ⎢ΨB> +
•  <ΨB ⎢ΨA>
•  = <ΨA ⎢ΨA> + <ΨB ⎢ΨB> + 2<ΨA ⎢ΨB>
= <ΨA ⎢ΨA> + <ΨB ⎢ΨB> + 2<ΨA ⎢ΨB>

ΨA and ΨB are normalized,

so <ΨA ⎢ΨA> = <ΨB ⎢ΨB> = 1

<ΨA ⎢ΨB> = <ΨB ⎢ΨA> = S,

S = Overlap integral.

∴ Denominator = 2(1 + S)
 Summing Up . . .
E = <ΨA+ΨB ⎢H ⎢ΨA+ΨB>/<ΨA+ΨB ⎢ΨA+ΨB>

Numerator = 2EA + 2 β
Denominator = 2(1 + S)
E+ = (EA + β)/ (1 + S)
Also E- = (EA - β)/ (1 – S)
E± = EA ± β
S is very small
∴ Neglect S
Energy level diagram
EA - β
β
ψA ψB
β

EA + β
 Linear combination of atomic orbitals

Rules for linear combination…..

1. Atomic orbitals must be roughly of the same energy.

2. The orbital must overlap one another as much as

possible- atoms must be close enough for effective
overlap.

3. In order to produce bonding and antibonding MOs, either

the symmetry of two atomic orbital must remain unchanged
when rotated about the internuclear line or both atomic
orbitals must change symmetry in identical manner.
 Rules for the use of MOs
* When two AOs mix, two MOs will be produced

* Each orbital can have a total of two electrons

(Pauli principle)

* Lowest energy orbitals are filled first (Aufbau

principle)

* Unpaired electrons have parallel spin (Hund s

rule)

Bond order = ½ (bonding electrons – antibonding

electrons)
 Linear Combination of Atomic Orbitals (LCAO)

The wave function for the molecular orbitals can be

approximated by taking linear combinations of atomic
orbitals.

A B
ψA ψB

ψAB = N(cA ψA + cBψB) c – extent to which each AO

contributes to the MO
ψ2AB = (cA2 ψA2 + 2cAcB ψA ψB + cB2 ψB 2)

Probability density Overlap integral

 Constructive interference

. + .
+. +.
ψg bonding
cA = cB = 1

ψg = N [ψA + ψB]
Amplitudes of wave
functions added
ψ2AB = (cA2 ψA2 + 2cAcB ψA ψB + cB2 ψB 2)
density between atoms

electron density on original atoms,

The accumulation of electron density between the nuclei put the
electron in a position where it interacts strongly with both nuclei.

Nuclei are shielded from each other

The energy of the molecule is lower

 node

+. -. +. .-
cA = +1, cB = -1 ψu
antibonding
ψu = N [ψA - ψB]

Destructive interference
Nodal plane perpendicular to the
H-H bond axis (en density = 0)
Energy of the en in this orbital is
higher.
ΨA-ΨB

Amplitudes of wave
functions
subtracted.
n The electron is excluded from internuclear region à destabilizing

Antibonding
 When 2 atomic orbitals combine there are 2
resultant orbitals
orbitals..
Eg.. s orbitals
Eg

σ*1s
E high energy antibonding orbital
1sb 1sa

σ1s

Molecular
orbitals
low energy bonding orbital
Molecular potential energy curve shows the variation
of the molecular energy with internuclear separation.
 Looking at the Energy Profile
•  Bonding orbital
•  called 1s orbital
•  s electron
•  The energy of 1s orbital
decreases as R decreases
•  However at small separation,
repulsion becomes large
•  There is a minimum in potential
energy curve
 H2

11.4 eV
LCAO of n A.O ⇒ n M.O.
109 nm

Location of
Bonding orbital
4.5 eV
 The overlap integral

n The extent to which two atomic orbitals on different atom

overlaps : the overlap integral

*
S = ∫ψ ψ B dτ
A
 S > 0 Bonding S < 0 anti

Bond strength depends on the

S = 0 nonbonding
degree of overlap
 Homonuclear Diatomics
•  MOs may be classified according to:
(i) Their symmetry around the molecular axis.
(ii) Their bonding and antibonding character.
•  σ1s< σ1s*< σ2s< σ2s*< σ2p< πy(2p) = πz(2p)
<πy*(2p) =πz*(2p)<σ2p*.
 dx2-dy2 and dxy

2-
Cl4Re ReCl4
 g- identical B
under inversion
A
u- not identical
Place labels g or u in this diagram

σ u

π g

πu

σg
 First period diatomic molecules
H H2 H σ1s2

σu*
Bond order: 1
Energy

1s 1s

σg

Bond order =
½ (bonding electrons – antibonding electrons)
 Diatomic molecules: The bonding in He2

He He2 He
σ1s2, σ*1s2

σu *

Bond order: 0
Energy

1s 1s

σg

Molecular Orbital theory is powerful because it allows us to predict whether

molecules should exist or not and it gives us a clear picture of the of the
electronic structure of any hypothetical molecule that we can imagine.
Second period diatomic molecules

Li Li2 Li σ1s2, σ*1s2, σ2s2

2σu* Bond order: 1

2s 2s
Energy

2σg

1σu*

1s 1s
1σg
Diatomic molecules: Homonuclear Molecules of the Second Period

Be Be2 Be

2σu*

2s 2s σ1s2, σ*1s2, σ2s2, σ*2s2

Energy

2σg
Bond order: 0

1σu*

1s 1s
1σg
Simplified
Simplified
MO diagram for B2

3σu*
1πg*

1πu
3σg
Diamagnetic??

2σu*

2σg
Li : 200 kJ/mol
F: 2500 kJ/mol
Same symmetry, energy mix-the one with higher energy moves higher
and the one with lower energy moves lower
 MO diagram for B2
B B2 B

3σu*
3σu*
1πg*

1πg*

2p (px,py)
1πu
3σg 2p
LUMO 3σg

2σu* HOMO 1πu

2σu*

2s 2s

2σg
2σg
Paramagnetic
C2

1πg 1πg

1πu
1πu

1σg
1σg

X
Paramagnetic ? Diamagnetic
 General MO diagrams

1πg 1πg

1πu
1πu

1σg 1σg

Li2 to N2 O2 and F2
Orbital mixing Li2 to N2
Bond lengths in diatomic molecules

Filling bonding orbitals

Filling antibonding orbitals

 Summary
From a basis set of N atomic orbitals, N molecular orbitals are
constructed. In Period 2, N=8.
The eight orbitals can be classified by symmetry into two sets: 4 σ
and 4 π orbitals.
The four π orbitals from one doubly degenerate pair of bonding
orbitals and one doubly degenerate pair of antibonding orbitals.

The four σ orbitals span a range of energies, one being strongly

bonding and another strongly antibonding, with the remaining
two σ orbitals lying between these extremes.

To establish the actual location of the energy levels, it is necessary

to use absorption spectroscopy or photoelectron spectroscopy.
Distance between b-MO and AO
 Heteronuclear Diatomics….

☛  The energy level diagram is not symmetrical.

☛  The bonding MOs are
closer to the atomic
orbitals which are
lower in energy.
☛  The antibonding MOs
are closer to those
higher in energy.
c – extent to which each atomic
orbitals contribute to MO
If cA>cB the MO is composed principally of φA
 HF
1s 1
2s, 2p 7

ψ =c1 φH1s + c2 φF2s + c3 φF2pz

Largely
2px and 2py
nonbonding
1σ2 2σ21π4
Polar
MO of CO molecule
 CO is a very good ligand!
How does it act?

O C

This lone pair is available for

donation to act as ligand.