Chapter 3: Orbitals and Bonding

Atomic Orbitals (AOs)

computer
calculated
2p orbital
electron configuration for atoms

1. Each electron is placed in the lowest-energy orbital available.

2. Each orbital can contain a maximum of two electrons with

opposite spins (Pauli exclusion principle).

3. When degenerate orbitals (orbitals with the same energy) are

available, the electrons first occupy them singly with the same
(parallel) spins. After all of the degenerate orbitals contain one
electron, additional electrons with opposite spins are added to
each (Hund’s rule).
Molecular Orbitals (MOs):
orbitals that extend around more than one atom

H:H
nuclei approach to bonding distance
1s atomic orbitals begin to overlap
electron waves reinforce to give lower energy MO (bonding)
or
electron waves cancel to give higher energy MO (antibonding)
These are sigma () MOs: symmetrical about the internuclear axis
Valence Bond Theory
overlap of AOs on two atoms at a time

forms localized MOs: extend around only two atoms

delocalized MOs: extend around more than two atoms

Generalizations for Simple MO Theory
1. two AOs overlap to form two MOs
number of MOs = number of AOs
2. lower energy MO (bonding)
higher energy MO with a node (antibonding)
3. use the same rules to assign electrons to MOs as used for AOs
fill lowest energy MO first
two electrons per MO (Pauli exclusion principle)
Hund’s rule

4. bond energy is approximately equal to the number of electrons

times E
5. magnitude of E increases with increasing overlap of the AOs
 H
CH4
H C H
methane
H

In the localized MO picture, there will be a bonding MO

and an antibonding MO for each C-H bond.

from experiments
all four C-H bonds are identical
geometry is tetrahedral

Therefore, methane must have four equivalent bonding MOs

with a tetrahedral arrangement.

use AOs from the valence shell of the atom to form the MOs
H 1s C 2s and three 2p
Hybridization of Atomic Orbitals
hybridize
2s and three 2p AOs four sp3 hybrid AOs
(4 AOs) (4 AOs)
(tetrahedral geometry)
Orbital Picture for a C-H Bond of Methane

*CH

CH

Use sp3 hybridization for all tetrahedral atoms.

 H H
H C C H ethane
H H
geometry at C’s tetrahedral
hybridization at C’s sp3
C-H bond formation just like methane
C-C bond formation sp3 AO on one C overlaps
with sp3 AO on the other C

free rotation about sigma bonds

H N H ammonia
H

geometry pyramidal (tetrahedral electron pairs)

hybridization at N sp3

N-H bond formation just like C-H of methane

unshared electron pair in a sp3 AO on N (a nonbonding AO)

 H H geometry at C’s trigonal planar (overall planar)
C C ethene
hybridization sp2
H H

2s and two 2p AOs three sp2 hybrid AOs

trigonal planar geometry
+ +
2p AO (perpendicular) 2p AO (perpendicular)

Use sp2 hybridization

for all trigonal planar atoms.
 The three sp2 AOs are used to form three sigma bonds
to each C (two C-H and one C-C).
The planes of both sets of sp2 AOs are the same
so these bonds are all in the same plane.
The remaining p orbital on each C is perpendicular to the
plane, so these p orbitals are parallel.

σCH

overlap of parallel p orbitals

σCC
pi bond (πCC)
π π
 H H
C C BDE = 145 kcal/mol ( and )
H H
H H
H C C H BDE = 81 kcal/mol ( only)
___
H H BDE = 64 kcal/mol ( only)

Rotation about a C=C requires about 60 kcal/mol.

At room temperature, there is approximately 20 kcal/mol
of energy available.
No rotation about C=C at room temperature.
H C C H ethyne
geometry at C’s linear
hybridization at C’s sp

2s and 2p two sp hybrid AOs (linear geometry)

+ two 2p orbitals + two 2p orbitals

Use sp hybridization for all linear atoms.

 sp2 sp sp
sp 2

sp3 H H H
H C C C C N
Csp3 + H1s H
nonbonding N sp
Csp + Nsp and two Cp + Np
Csp2 + Csp2 and Cp + Cp
Csp3 + Csp2
Resonance and MO Theory
Resonance and delocalized MOs (around more than two atoms)
are just different ways to describe the same types of bonds.
sp2

formate ion

sp2
atom with unshared pair
next to pi bond puts pair
sp2
in p orbital

Resonance is stabilizing.
conjugated molecule: a molecule that has a series of three
or more overlapping parallel p orbitals
on adjacent atoms
Rules for Resonance Structures
Rule 1: In drawing resonance structures, the nuclei of atoms
may not be moved; only pi and nonbonding electrons in conjugated p
orbitals may be moved.

H3C C
O ? H3C C
O H
H has moved
O H O

Rule 2: Each structure must have the same number

of electrons and the same total charge.
Rule 3: The relative stability of resonance structures is judged
by the same rules used to judge the stability of Lewis structures:

octet rule
number and location of formal charges
interaction between charges

_ H + _
H + _ H +
C N N C N N C N N
H H H
more important less important unimportant
- charge on more (octet rule)
electronegative N
Arrows always point from where the electrons are in a structure
to where they are going in the next structure.
Rule 4: The actual structure most resembles
the most stable resonance structure.

Rule 5: The resonance stabilization energy increases

as the number of important resonance structures increases.
Types of Resonance Interactions
Electron Pair Next to Pi Bond
_
O O
H3C C H3C C
sp2 O _ O
acetate anion
same number of electrons
same total charge -1
structures are equivalent, so identical energies
contribute equally to the resonance hybrid
two equally important structures means
a large resonance stabilization
 _
O O
H3C C H3C C acetic acid
OH OH
+
more important less important
fewer formal charges
actual structure more
like this one

smaller resonance stabilization

 _
O O
_
C C
H3C CH2 H3C CH2

somewhat more stable

sp2
negative on more
electronegative atom

significant resonance stabilization

 O O O O O
_ _
_
C C C C C
H3C CH2 H3C CH CH3 H3C CHCH2 CH3

_
_ O O
O this C interrupts
C C
C H3C CH CH3 the conjugation
H3C CH2

_
O O
C C
H3C CH CH3
 One Electron Next to Pi Bond

sp2
H H
H C H H C H
C C C C
H H H H
allyl radical
two equivalent structures, so large resonance stabilization
H H H H
H C C H C C C H
H H H H H

BDE = 98 kcal/mol BDE = 85 kcal/mol

 Empty Orbital Next to Pi Bond

sp2

H H H H H H
H C C + H H C + C H H + C C H
C C C C C C C C C
H H H H H H H H H

three very similar resonance structures,

so large resonance stabilization
Pi Bond Between Atoms of Different Electronegativities

_ +
O O O
C C C
H3C H H3C + H H3C _ H
no octet
major contributor minor contributor

_
H H H H
C C
C C
H H H + H
unimportant
 Cycle of Pi Bonds

benzene

two equivalent structures, so large resonance stabilization

Combinations

_ _
O O O O
_

large resonance stabilization O

_
 these electrons are not
N
part of the conjugated system

N these electrons are part

of the conjugated pi system
H

_
N N
etc.
N N+
H H