CHM574'

INORGANIC'CHEMISTRY'II'

Chapter'1:'Molecular'Orbital'Theory'
 Content'in'Molecular'Orbital'Theory'
•  Orbital'shapes'and'energies'(s,'p,'d)'
•  Type'of'molecular'orbitals'and'combinaJons'
•  Homonuclear'diatomic'molecules'(2nd'period)'
•  Heteronuclear'diatomic'molecules''
•  Bond'order,'bond'energy'and'bond'length'
•  MetalMcarbon'bonds'in'carbonyl'complexes'
Orbital'shapes,'Individual'(“isolated”)'Atoms'

all s orbitals

all p orbitals

d orbitals
 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Theories of Covalent Bonding

Ref: Silberberg 4th ed. 2006. Mc Graw Hill

11-1
 Theories of Covalent Bonding

1 Valence Bond (VB) Theory and Orbital Hybridization

2 The Mode of Orbital Overlap and the Types of Covalent Bonds

3 Molecular Orbital (MO)Theory and Electron Delocalization

Figure 11.8
The conceptual steps from molecular formula to the hybrid orbitals
used in bonding.

Step 1 Step 2 Step 3

Molecular shape
Molecular Lewis and e- group Hybrid
formula structure arrangement orbitals

Figure 10.1 Figure 10.12 Table 11.1

 Predicting Hybridization
Schemes
1. Write a Lewis structure for the molecule or ion.
2. Use the VSEPR method to predict the electron-
group geometry of the central atom.
3. Select the hybridization scheme that corresponds
to the VSEPR prediction.
4. Describe the orbital overlap and molecular
geometry.
 Figure 11.9 The s bonds in ethane(C2H6).

both C are sp3 hybridized

s-sp3 overlaps to s bonds

sp3-sp3 overlap to form a s bond

relatively even
distribution of electron
density over all s
bonds
Carbon–Carbon Double Bonds

A double bond is
made up of one
sigma bond and one
pi bond

EOS
 Carbon'carbon)triple)bond)
Figure 11.11 The$σ$and$π$bonds$in$acetylene$(C2H2).$

overlap)in)one)posi2on)')σ

p)overlap)')π
 MOLECULAR ORBITAL
THEORY
(delocalized electron model)
 localized electron model

Lewis model, Valence Bond Theory and

Hybridization
• Interpret the structure and bonding of
molecules.
• (Problem?????)
• cannot explain some of the experimental
observations made on certain molecules (diff
conclusion)
 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Problems with the localized electron

model:
• No direct information on bond energies.[model does
not deal with single (unpaired electrons) and assumes
totally localized electrons]
• Assumes that all electrons are localized (staying at
one place), therefore a concept of resonance must be
added.
• Does not deal effectively with molecules containing
unpaired electron, cannot explained the paramagnetic
property of the O2 molecules.

11-9
 CASE

• Oxygen was once thought to be diamagnetic

(no unpaired electron, Lewis structure: not
atrracted to magnets), and dioxygen is
observed to be paramagnetic (has at least one
unpaired electron and therefore attracted to
magnets), and a new revised molecular orbital
(MO) model confirmed oxygen's paramagnetic
nature.
Figure 11.22

The paramagnetic
properties of O2
 Delocalization and Shapes of Molecular
Orbitals
• Valence bond theory also describes
resonance formulas.
– Carbonate ion (CO32-) is an example.

12
Delocalization and CO32-

13
• Molecular orbital theory describes shapes in
terms of delocalization of electrons.

14
 Resonance

resonance structures reflect the structure of the

molecule or ion.
localized Electrons model: Resonance

In reality, each of the four atoms

in the nitrate ion has a p orbital.
The p orbitals on all three
oxygens overlap with the p orbital
on the central nitrogen.
The electrons are not localized
between the nitrogen and one of
the oxygens, but rather are
delocalized throughout the ion.
 Resonance

The organic molecule

benzene has six s bonds
and a p orbital on each
carbon atom.
 Resonance

• In reality the electrons in benzene are not localized,

but delocalized.
• The even distribution of the electrons in benzene
makes the molecule unusually stable.
•Sigma bonds can be described as being localized
•Pi bonding must be treated as being delocalized
Figure 11.25

The lowest energy -bonding MOs in benzene and ozone.

benzene, C6H6 ozone,O3

Figure 10.1
The steps in converting a molecular formula into a Lewis structure.

Place atom
Molecular
Step 1 with lowest
formula
EN in center
Atom Add A-group
Step 2
placement numbers

Sum of Draw single bonds.

Step 3
valence e- Subtract 2e- for each bond.
Give each
Remaining
Step 4 atom 8e-
valence e-
(2e- for H)

Lewis
structure
Figure 10.12
The steps in determining a molecular shape.

See Figure
Molecular
Step 1 10.1
formula

Lewis Count all e- groups around central

Step 2
structure atom (A)

Electron-group Note lone pairs and double

Step 3
arrangement bonds
Count bonding and
Bond
Step 4 nonbonding e-
angles
groups separately.

Molecular
shape
(AXmEn)
 Summary of Concepts

• The VSEPR method is used to predict the shapes

of molecules and polyatomic ions
• If all electron groups are bonding groups, the
molecular geometry is the same as the electron-
group geometry
• A polar covalent bond has separate centers of
positive and negative charge, creating a bond
dipole
EOS
 Summary of Concepts

• In the valence bond theory, a covalent bond is

formed by the overlap of atomic orbitals of the
bonded atoms in a region between the atomic
nuclei
• Hybridized orbitals include sp, sp2, sp3, sp3d, and
sp3d2

• Unhybridized p orbitals overlap in a side-by-

side fashion to form bonds
EOS
 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Summary (cont.)

• Single bonds are all hybridized s bonds, double

bonds have one s bond and one bond, and triple
bonds have one s bond and two bonds
• In molecular orbital theory, atomic orbitals of
separated atoms are combined into molecular
orbitals
• The benzene molecule is usually represented by its
resonance hybrid
• Benzene-like compounds are called aromatic
compounds
EOS

11-25