Electronic Structure & Covalent

Bonding

Roldan M. de Guia
Department of Biochemistry
Faculty of Pharmacy
University of
Santo Tomas
2009
 ORGANIC CHEMISTRY
the study of compounds of carbon
there are over 10 million organic
compounds

(S)-((S)-1-((2S,3S)-3-hexyl-4-oxooxetan-2-yl)tridecan-2-yl) 2-formamido-
4-methylpentanoate
ATOMIC STRUCTURE
 ELECTRON CONFIGURATION
Pauli Exclusion Principle
 Orbitals can contain a maximum of two electrons which
must be of opposite spin

ms = +½ ms = -½
 ELECTRON CONFIGURATION
Aufbau Principle
 Atomic orbitals are filled with electrons from lowest
potential energy to highest.
 ELECTRON CONFIGURATION
Madelung’s Rule
 Orbitals fill with
electrons as n + l,
where n is the principle
quantum number and l
is the angular
momentum quantum
number
 explains why the 4s
orbital has a lower
energy than the 3d
orbital
 gives the periodic table
its characteristic
appearance
“Fill up” electrons in lowest energy orbitals (Aufbau principle)

? ?

Li
Be
B
C5 6
34electrons
electrons
BBe
Li1s1s
1s
2s2s
2s2p
2 22 2 12 1

H
He12electron
electrons

He
H 1s
1s12
The most stable arrangement of electrons in subshells is
the one with the greatest number of parallel spins
(Hund’s rule).

F
N
O
Ne
C96
7
810
electrons
electrons
electrons
Ne
C
N
O
F 1s
1s
1s222s
2s
2s22p
2 2
2p
2p2346
2 5
 CHEMICAL BONDING
Electronic Electronic Lewis Dot
Atom
Structure Configuration Structure
3p

3s

B
2p
Boron 2 2 1
1s 2s 2p 2s

1s

3p

3s

Phosphorus [Ne] 3s23p3

2p

2s
P
1s
 CHEMICAL BONDING – Octet
Rule

-
Li+ + F Li+ F -
IONIC BONDING
Na Na + 1e

Cl + 1 e Cl
COVALENT BONDING

σ*

Eσ*

1s 1s

Eσ

σ
 COVALENT BONDING

 F2 F F A nonpolar covalent
bond

 HF H F A polar covalent bond

δ+ δ−
CLASSIFICATION OF CHEMICAL
BONDS
 CLASSIFICATION OF CHEMICAL
BONDS
Difference in
Electronegativity Most Likely Formed
Type of Bond
between Bonded Between
Atoms
<0.5 Non-polar covalent 2 non-metals or a
non-metal & a
0.5 – 1.9 Polar covalent metalloid

A metal & a non-

>1.9 Ionic
metal

 Care must be taken to distinguish between polar bonds

and polar molecules!!
MOLECULAR GEOMETRY -
VSEPR
 POLARITY OF BONDS

O O
H Cl H H
C
H C CH
3 3
 Care must be taken to distinguish between polar bonds
and polar molecules!!
Carbon dioxide:

O C O
 LEWIS STRUCTURE
F N F O C O

F O

H
H C O H C O
H

formal total
total

( )
total 1
charge on = number of
an atom in a valence - number of - 2
number of
bonding
electrons in nonbonding
Lewis electrons
the free electrons
structure
atom
RESONANCE STRUCTURE
one of two or more Lewis structures for a single molecule that cannot be
represented accurately by only one Lewis structure.
+ - - +
O O O O O O
FORMAL CHARGE = 0
 Diazomethane, CH2N2

H H
C N N or C N N
H H

• Nitromethane, CH3NO2

H O H O
H C N O or H C N O
H H
STRUCTURES & FORMULAE
MOLECULAR MODELS
HYBRIDIZATION OF ORBITALS

CH4
HYBRIDIZATION OF ORBITALS
sp2 HYBRID ORBITALS

H H
Ethene C C
H H

H H

C C

H H
sp2 HYBRID ORBITALS
sp2 HYBRID ORBITALS
sp2 HYBRID ORBITALS
sp HYBRID ORBITALS
Acetylen
e
sp HYBRID ORBITALS
sp HYBRID ORBITALS: CO2
O C O

O C O

O C O
Lengths of Covalent Bonds
Bond
Bond Length
Type
(pm)
C-C 154
C= C 133
C≡ C 120
C-N 143
C= N 138
C≡ N 116

Bond Lengths
Triple bond < Double Bond < Single Bond
BOND LENGTH & STRENGTH
 Effect of Hybridization on Bond Length & Strength
BOND
BOND TYPE BOND
# of π BONDS ENERGY,
C –C LENGTH, pm
kcal/mole
sp3 – sp3 0 154 82.76

sp3 – sp2 0 153 85.48

sp3 – sp 0 146 91.58

sp2 – sp2 1 147 91.42

sp2 – sp 0 142 96.48

sp – sp 2 138 103.60

↑ s character = ↓ bond length = ↑ bond strength

 Comparison of Bond Length of C to C Bonds involving Hybrid Orbitals

BOND TYPE BOND LENGTH, pm

Ethane CH3 – CH3 sp3 – sp3 153.8

Propylene CH3 – CH = CH2 sp3 – sp2 150.1

Methylacetylene CH3 – C ≡ CH sp3 – sp 145.9

Ethylene CH2 = CH2 sp2 – sp2 133.9

Acetylene CH ≡ CH sp – sp 120.7
FUNCTIONAL GROUPS
FUNCTIONAL GROUPS