VALENCE BOND THEORY & VSEPR:

Valence bond theory and Valence Shell Electron Pair Repulsion theory (VSEPR) are simple
but effective models for understanding the bonding that occurs in organic compounds.
 Covalent bonds are usually formed between two atoms by the overlap of 2 half-filled
(singly-occupied) orbitals of the bonding atoms. For example, two hydrogen atoms form a
covalent bond by the overlap of their half-filled 1s atomic orbitals.

H + H H H H H

1s1 1s1

Valence Bond theory predicts that This H 2 molecule is stable (low Each H atom in
two, half-filled 1s atomic orbitals in energy) because the electrons H2 is isoelectronic
of hydrogen overlap to form a single spend most of their time between with Helium
(sigma) bond. H nuclei-drawing them together.
 Carbon is in group IVA of the periodic table and therefore has 4 valence (bonding)
electrons, i.e., 4 electrons in its highest Principal Energy Level (PEL). Its ground state
electron configuration is given as …
1s2 2s2 2px1 2py1 2pz0

4 valence electrons
 Carbon normally forms 4 covalent bonds using its 4 valence shell electrons, however, its
ground state electron configuration is not suitable for this because the 2s orbital is full and
the 2pz orbital is empty. In a process called ‘hybridization’, one of the 2s electrons is
promoted to the vacant 2pz orbital producing 4 half-filled orbitals. These orbitals alter
their shape in order to achieve the best possible overlap with orbitals from other atoms and
also to move as far away from each other as possible.
hybridization
1s2 2s2 2px1 2py1 2pz0 1s2 2s1 2px1 2py1 2pz1

 Only the outer, valence electrons are involved in bonding and thus the inner shells of
electrons will not be considered further.
 The vast majority of organic compounds are formed from just a few elements, i.e., C, N, O,
P, S and the halogens. We will look at their hybridization states in the following pages.

ORGANIC CHEMISTRY INTRO 1

BONDING IN CARBON COMPOUNDS 6 The arrangement of the 4 atomic
C orbitals and the electronic
configuration in the carbon atom
orbital shape are not suitable to form 4 bonds.
Group 4A
4 valence e’s. A change (hybridization) occurs
2s2 2px1 2py1 2pz0
Covalence = 4 ground state to the orbital shape and electronic
valence electron configuration to facilitate bonding.
configuration The 3 hybridizations occurring in
cabon are shown below.

sp 2 hybridized sp hybridized
(triangular planar) (linear)
sp 3 hybridized (tetrahedral)
Carbon forms a double bond Carbon forms 1 triple or 2 double bonds
Carbon forms 4 single bonds

90º 180º
109.5º 120º
or C C
C C

orbital
shape
(sp2 orbitals x 3) + (p x 1)
hybridized
orbitals (sp3 orbitals x 4) (sp orbitals x 2) + (p x 2)

electron
configuration (3  bonds) + (1  bond)

bonds (forms 4  bonds) alkenes and arenes (2  bonds) + (2  bonds)

alkanes e.g., ethene and benzene alkynes
e.g., ethane (C 2H6) (C 2H4) (C 6H6) e.g., acetylene (C 2H2)
H
H H H
H H H
H H C H C
H
C H C C H C H C
H H H H
H H
C H H
H
H H H C C H
H H H H
C C H H also CO2
H H H O C O

ORGANIC CHEMISTRY INTRO 2

BONDING IN NITROGEN COMPOUNDS 7 The shape and orientation of the
N 4 atomic orbitals in the nitrogen
atom are not suitable for forming
Group 5A orbital shape 3 (or 4) bonds.
5 valence e’s.
Covalence = 3
2s2 2px1 2py1 2pz1 A change (hybridization) occurs
ground state to the orbital shape to facilitate
valence electron bonding. The 3 hybridizations
configuration occurring in nitrogen are shown
below.

sp 3 hybridized sp 2 hybridized sp hybridized

Nitrogen forms 3 or 4 single bonds Nitrogen forms a double bond Nitrogen forms 1 triple bond
...... ....
90º 180º

N
or
N .:. N 120º
.. N

107º
..
orbital
.... ..
shape

hybridized (sp 2 orbitals x 3) + (p x 1)

orbitals (sp3 orbitals x 4)
(sp orbitals x 2) + (p x 2)
electron
configuration
bonds (1 lone pair) + (2  bonds) + (1  bond)
1 lone pair (4  bonds) (1 lone pair) + (1  bond) + (2  bonds)
+ or azo compounds
nitriles
H e.g., (trans azobenzene)
Cl -
3  bonds e.g., ethanenitrile
.... .. ..
+ N N
N N
H CH3
H H H C
H ..:
....
H
N N
amines
ammonia
ammonium
chloride
N
.:.
NH3 NH4+Cl- :N C CH3

ORGANIC CHEMISTRY INTRO 3

BONDING IN OXYGEN COMPOUNDS 8 The shape and orientation of the
O 4 atomic orbitals in the oxygen
atom are not optimal for forming
orbital shape 2 (or 3) bonds.
Group 6A
6 valence e’s.
A change (hybridization) occurs
Covalence = 2 2s2 2px2 2py1 2pz1
ground state to the orbital shapes to facilitate
valence electron bonding. The 2 hybridizations
configuration occurring in oxygen are shown
below.

sp 3 hybridized sp 2 hybridized
Oxygen forms 2 single bonds Oxygen forms a double bond

90º
105º
or

..
O .... O .:. O
: 120º
.. ....
.. .. .. ..
orbital
shape

hybridized
orbitals (sp3 orbitals x 4) (sp 2 orbitals x 3) + (p x 1)
electron
configuration
bonds (2 lone pair) + (1  bonds) + (1  bond)
2 lone pair 1 lone pair
+ or + O
2  bonds 3  bonds e.g., acetone (CH3CCH3)
: O:
hydronium ion (H3O+)
..:
e.g., methanol (CH 3OH)
CH3 H O
..: C
H3C CH3
+ C
.... O .. O H 3C
.... H
H
H CH 3

ORGANIC CHEMISTRY INTRO 4

 Note that a double bond is made of one  and one  bond.
 Note that a triple bond is made of one  and two  bonds.
 Halogens (groups VIIA elements) generally form only one  bond in organic compounds.
They do not reshape their orbitals (hybridize) when they bond.
17 The shape and orientation of the
Cl 4 atomic orbitals in the halogens
are adequate for forming one
orbital shape
single bond.

ground state Hybridization does not occur

3s2 3px2 3py2 3pz1
valence electron when halogens form single
configuration bonds.

(3 lone pairs and 1  bond)

..
H : Cl
.. CH3

Cl C H methyl chloride
(chloromethane)
H
 Hydrogen, like the halogens, does not hybridize its 1s orbital when bonding.
 Silicon, like carbon, is a group 4A element with 4 valence electrons. As expected, silicon forms
sp3 hybridized tetrahedral compounds with 4 substituents. Simple examples include silicon
tetrabromide (SiBr4) and tetramethylsilane [(CH3)4Si]. Silicon forms a few compounds in which
it has double bonds, e.g., H2Si=CH2. However, silicon's large size makes p-orbital overlap for 
bonds less effective than in carbon compounds. Unlike 2nd period elements which cannot
accommodate more than 8 electrons in their valence orbitals, Si, a 3rd period element can expand
its valence shell to accommodate 10 electrons (sp3d hybridized – 5 substituents, e.g., SiF5-) and
even 12 electrons (sp3d2 hybridized – 6 substituents, e.g., fluorosilicic acid, H2SiF6).
 Phosphorus, like nitrogen, is a group 5A element with 5 valence electrons. As expected,
phosphorus forms sp3 hybridized compounds with 3 substituents. Simple examples include
phosphorus tribromide (PBr3) and trimethylphosphine [(CH3)3P]. Phosphorus forms some
compounds in which it has double bonds to oxygen, e.g., phosphoric acid (H3PO4). However,
phosphorus’ large size makes p-orbital overlap for  bonds less effective than in C or N
compounds. Like other 3rd period elements, phosphorus can be bonded to 4, 5, and 6 atoms.
e.g., phosphorus oxychloride (Cl3P=O), phosphorus dibromide trichloride (PBr2Cl3), and
phosphorus hexafluoride anion (PF6-).
 Sulfur, like oxygen, is a group 6A element with 6 valence electrons. As expected, sulfur forms
sp3 hybridized compounds with 2 substituents. Simple examples include dimethyl sulfide
[(CH3)2S] and methyl mercaptan (methane thiol) (CH3SH). Sulfur can form bonds to three
(H2SO3), four (H2SO4), five (SOF4) and six atoms (SF6).
 A methyl cation has an sp2 hybridized carbocation with a vacant p orbital. A methyl radical has
an sp2 hybridized carbon atom with a ½-filled 2p orbital. A methyl anion contains an sp 3
hybridized carbanion with a lone pair in one of its sp3 orbitals. Draw them.

ORGANIC CHEMISTRY INTRO 27

In saturated compounds, all atoms have only  bonds, whereas in unsaturated compounds, one
or more  bonds are present.
 Conjugated unsaturation occurs when alternating  and  bonds are present. In such
compounds, all p-orbitals in conjugated  bonds overlap.
1,3-butadiene CH2 CH CH CH2

H
H
H C C O
C C H
H H
H
H
H C C
C C H 2-cylcopentenone
H H
 Isolated unsaturation occurs when  bonds are separated by more than one  bond.
In such compounds, p-orbitals of one  bond cannot overlap with p-orbitals of other 
bonds.
1,4-pentadiene CH2 CH CH2 CH CH2

H H
O
H C H
C C C C
H H H H

H H 3-cylcopentenone
H C H
C C C C
H H H H

 Cumulated unsaturation describes immediately adjacent unsaturation. Cumulated

carbon-to-carbon compounds are not very stable and are rarely encountered.

1,2-butadiene H2C C CH CH3

ORGANIC CHEMISTRY INTRO 28

 HYBRIDIZATION STATE IS BASED ON THE NUMBER OF REGIONS OF ELECTRON DENSITY

Be B C N O F

.. ..
O C O H C N :
sp H Be H .. ..

H C C Na+
..
N N
..
N
-
H
.. + ..
sodium azide

H H ..
C C ..
N O H :
H .. ..
H H H -: O.. : C O
HO
B .. ..
sp2 O.. H .. + H :
.. O N
H O C .. ..
.. .. OH
O H ..
..
.. ..

N O
H - H H H H :
H H
sp3 B C ..
H H H + +
H H
H H
N O
Na+BH4-
H H H
H
H H

NH4+Cl- hydronium ion

Mg Al Si P S Cl

sp

H H ..
H H
:O : :O:
Al C Si P CH2 ..
sp2 S
H H H3C
H
:O : S
:O: :O:

:O :
:O :
.. Cl
:O : S .. O ..
HO .. ..O
- HO .O
. HO
H P
OH HO :O :
OH :O :
sp3 Al HO
H Si .. Cl
H
H HO S : ..
OH
HO HO : HO ..O
Li +
AlH4- P .. HO
Cl Cl : .. :O :
Cl ..
Cl
S :
Cl :
Cl : HO
ORGANIC CHEMISTRY INTRO 29
Study the following table. In the last 3 columns Lewis structures are drawn as if the
atoms were bonded. Learn these names and structures and identify their hybridization
states.

Lewis # # #
valence unshared
Symbol bonds
e- 's + 1 F.C. neutral - 1 F.C.
e- 's

-
B
B 3 3 0 none B
boride ion
..
+
C
C C-
C 4 4 0 carbonium
ion carbide ion

.. ..
+ -
N
N N
N 5 3 2 :
nitronium
ion nitride ion
.. ..
..

O+ O-
O :
O 6 2 4 : ..
oxonium
ion an oxide ion

.. .. -
.. ..
F+ :
: .. F .. F
F 7 1 6 ..
unhybridized unhybridized
fluoronium ion fluoride ion
..
..
.. -
Cl + .. Cl ..
Cl 7 1 6 :
.. Cl
:
.. unhybridized
Bromine and iodine are analogous to fluorine and chlorine. Draw the structures of
chloronium ion unhybridized
bromonium and iodinium cations, bromide and iodide anions, and bromine and iodine.
chloride ion

ORGANIC CHEMISTRY INTRO 30