Molecular Geometry

and Bonding Theories

Two Simple Theories of
Covalent Bonding
 Valence Shell Electron Pair Repulsion
Theory
 VSEPR
 R. J. Gillespie - 1950’s
 Valence Bond Theory
 Hybridized orbitals
 L. Pauling - 1930’s & 40’s
Stereochemistry
 Study of the 3 dimensional shapes of molecules
 TWO MODELS
 VSEPR Theory
 Valence Bond Theory

 Some questions to examine:

Why are we interested in shapes?
What role does molecular shape play in life?
How do we determine molecular shapes?
How do we predict molecular shapes?
Determining Molecular Structure
 Draw the Lewis dot structure
identify central atom
 Count # of regions of high electron
density on central atom
 VSEPR tells the geometry around
central atom
Determining Molecular
Structure
 Identify lone pair effect on ideal
molecular geometry
 Repeat procedure for more than one
central atom
 Determine polarity from entire molecular
geometry
 electronegativity differences
VSEPR Theory
 regions of high electron density around the
central atom go as far apart as possible to
minimize repulsions
 five basic shapes
 based on # of regions of high electron density
 several modifications of these five basic
shapes will also be examined
VSEPR Theory

Two regions of high electron density

VSEPR Theory
Three regions of high electron density
VSEPR Theory
Four regions of high electron density
VSEPR Theory

Five regions of high electron density

VSEPR Theory

Six regions of high electron density

VSEPR Theory
 electronic geometry (electron domain)
 determined by the locations of regions of high
electron density around the central atom(s)
 molecular geometry
 determined by the arrangement of atoms
around the central atom(s)
 electron pairs are not used in the molecular
geometry determination
VSEPR Theory
 CH4 - methane
 electronic geometry
bond angles = 109.5o
tetrahedral
 molecular geometry
tetrahedral
VSEPR Theory

 H2O - water
 electronic geometry
tetrahedral bond angle = 104.50
 molecular geometry
bent or angular
VSEPR Theory

 lone pairs of electrons (unshared pairs)

require more volume than shared pairs
 there is an ordering of repulsions of
electrons around central atom
VSEPR Theory
1 lone pair to lone pair repulsion is strongest
2 lone pair to bonding pair repulsion is
intermediate
3 bonding pair to bonding pair repulsion is
weakest
 mnemonic for repulsion strengths
lp/lp > lp/bp > bp/bp
 lone pair to lone pair repulsion is why bond
angles in water are less than 109.50
 Valence Bond Theory
 covalent bonds are formed by overlap of
atomic orbitals
 atomic orbitals on the central atom can mix
and exchange their character -
hybridization
 common hybrids
pink flowers, mules, corn, grass
 Valence Bond Theory
 hybridized orbitals describe same shapes
as VSEPR
 Name of orbital Shape of orbital
sp3 tetrahedral
sp2 trigonal planar
sp linear
sp3d trigonal bipyramidal
sp3d2 octahedral
Hybrid Orbitals

 Electronic Structures Lewis

Formulas Be ··
1s 2s 2p
Be   ·· .
·· C l
3s 3p ··
Cl [Ne]  
Hybrid Orbitals
 Dot Formula Electronic Geometry
·· ··
·· Cl ·· Be ·· Cl ··
·· ·· ·· ··
··Cl Be Cl ··
·· ··
180o - linear
Hybrid Orbitals
 VSEPR Polarity
Cl - Be - Cl
Cl·· Be ·· Cl Electroneg ativities 3.5
 1.53.5
 
2.0 2. 0

180o-linear very polar bonds

Hybrid Orbitals
 VSEPR Polarity
Cl - - - Be - - - Cl
 
Cl·· Be ·· Cl
bond dipoles are symmetric
180o-linear
nonpolar molecule
Hybrid Orbitals
 Molecular Geometry

same as electronic geometry

symmetrical & nonpolar
Hybrid Orbitals

 Valence Bond Theory (Hybridization)

1s 2s 2p 1s sp hyb 2p
Be   
3s 3p
Cl [Ne]  
Hybrid Orbitals Linear
Hybrid Orbitals

 examples
BF3, BCl3
 all are trigonal planar, nonpolar
molecules
Hybrid Orbitals

 Electronic Structures Lewis

··
Formulas B.
1s 2s 2p
B   ·· .
·· Cl
3s 3p ··
Cl [Ne]   
 Hybrid Orbitals

 Dot Formula Electronic Geometry

··
·· Cl ··
··
·· ··
·· · B · ·· B
·· Cl · · Cl ··
·· ··
··
120-trigonal planar
Hybrid Orbitals

 VSEPR Polarity
B - Cl
Electroneg ativities 1.5
3.0

Cl Cl 1.5
B
v ery polar bonds
Cl
120-trigonal planar
Hybrid Orbitals

 Molecular Geometry
Hybrid Orbitals

 Valence Bond Theory (Hybridization)

2
1s 2s 2p 1s sp hybrid
B    
5s 5p
Cl [Ne]   
Hybrid Orbitals Trigonal Planar
Hybrid Orbitals

 examples
CH4, CF4, CCl4, SiH4, SiF4
 all are tetrahedral, nonpolar molecules
 as long as they have the same 4 substituents
Hybrid Orbitals

 Electronic Structures Lewis Formulas

2s 2p ..
C [He]  .C .
Hybrid Orbitals

 Electronic Structures Lewis Formulas

2s 2p ..
C [He]  .C .
1s
H H.
Hybrid Orbitals
 Dot Formula Electronic Geometry
..
H
.. C
.. .. .. ..
H C.. H
..
H tetrahedral
109.5o bond angles
Hybrid Orbitals

 VSEPR Polarity
H C - H
C Electronegativities 2.5
 2.1

H H 0.4
H
slightly polar bonds
tetrahedral
Hybrid Orbitals

 Molecular Geometry
Hybrid Orbitals

 Valence Bond
2s 2p four sp3 hybrid orbitals
C [He]  C [He]
1s
H
Hybrid Orbitals Tetrahedron
Hybrid Orbitals

 Examples
PF5, AsF5, PCl5, etc.
 All are trigonal bipyramidal, nonpolar
molecules.
Hybrid Orbitals

 Electronic Structures Lewis Formulas

4s 4p ··
. As .
As [Ar] 3d10  .
2s 2p
·· ··
F .
F [He]  
··
Hybrid Orbitals

 Dot Formula Electronic Geometry

·· ··
·· F ·· ··
·· ··
·· · F ·· ·· As ·
·· F · As · ·· ·
· ··
·· ·· ·· F ·· ··
·· F · ··
·
·· trigonal bipyramidal
Hybrid Orbitals

 VSEPR Polarity
··
·· F ·· ·· As - F
·· F ··
·· F As ·· ·· · Electroneg ativities 2.1
4.0

·· F· 1.9
··
·· F ··
··
very polar bonds
trigonal bipyramid
Hybrid Orbitals

 VSEPR Polarity
·· ··
·· F ·· ·· · F · ··
F ·· · ·
··
·· F As ·· ·· F ··
·· · · F As ·· ·· ·
·· F· ·
·· ·· F·
·· F ·· ··
·F· ·
·· · ··
trigonal bipyramid
symmetric dipoles cancel
nonpolar molecule
Hybrid Orbitals

 Molecular Geometry
 Hybrid Orbitals

 Valence Bond (Hybridization)

4s 4p 4d
As [Ar] 3d10  _______________

five sp3 d hybrids
Hybrid Orbitals
Trigonal Bipyramidal Molecules

 Valence Bond (Hybridization)

Hybrid Orbitals
Trigonal Bipyramid Molecules
 Valence Bond
(Hybridization)
Variations of Trigonal
Bipyramidal Shape
 If lone pairs are incorporated into the
trigonal bipyramidal structure, there are
three possible new shapes.
 One lone pair - seesaw shape
 Two lone pairs - T-shape
 Three lone pairs - linear
Hybrid Orbitals

 Example
SF6, SeF6, SCl6, etc.
 These are octahedral and nonpolar
molecules.
 if all 6 substituents are the same
Hybrid Orbitals
 Electronic Structures Lewis Formulas
4s 4p ··
·· Se .
Se [Ar] 3d10   .
2s 2p
··
F [He]   ·· F .
··
Hybrid Orbitals
 Dot Formula Electronic Geometry
·· ··
·· F ··
·· ·· ·· ··
·· F ·· ·· ·· F ··
·· ·· Se
·· Se ·· · ·· ··
·· F ·· ·· F·
·· ··
·· ·· F ·· ··
·· octahedral
Hybrid Orbitals
 VSEPR Polarity
F Se - F
F F
Se
Electroneg ativities 2.4
4.0

F F 1.6

F v ery polar bonds

octahedral
Hybrid Orbitals
 VSEPR Polarity
F F
F F F
F
Se Se
F F F
F
F F

octahedral symmetric dipoles cancel

nonpolar molecule
Hybrid Orbitals
 Molecular Geometry
Hybrid Orbitals
Octahedral Molecules
 Valence Bond (Hybridization)
4s 4p 4d
Se [Ar] 3d10   __________

six sp3 d2 hybrids
Hybrid Orbitals
Octahedral Molecules
 Valence Bond (Hybridization)
AB6- No Lone Pairs -
Octahedral Molecules
Variations of Octahedral Shape
 If lone pairs are incorporated into the
octahedral structure, there are two
possible new shapes.
 One lone pair - square pyramidal
 Two lone pairs - square planar
Compounds Containing
Double Bonds
 Ethene or ethylene is the simplest double
bond containing organic compound.
 Lewis Dot Formula for ethene C2H4
 N = 2(8) + 4(2) = 24
 A = 2(4) + 4(1) = 12
S = 12
Compounds Containing
Double Bonds
 Lewis Dot Formula for ethene C2H4

H· · H H H
· ·
C ·· ·· C or C C
·
H· ·· H
H H
Compounds Containing
Double Bonds
 VSEPR
suggests C atoms at center of two equilateral
triangles
H H

C C

H H
Compounds Containing
Double Bonds
 Valence Bond Theory
sp2 hybrids for the C atoms
1 electron remains in an unhybridized p orbital
2s 2p three sp2 hybrids 2p
C  
Compounds Containing
Double Bonds
 C atoms are sp2 hybridized with single
electrons in each of the lobes
Top view
Compounds Containing
Double Bonds
 The unhybridized 2p orbital on the C atom lies
perpendicular to the planar sp2 lobes.
Side view
Compounds Containing
Double Bonds

 C=C double bond results from head-on overlap

of two sp2 hybrid orbitals
Compounds Containing
Double Bonds
 The portion of the double bond formed from the head-on
overlap of the sp2 hybrids is designated as a s bond.
Compounds Containing
Double Bonds
 The other portion of the double bond, resulting
from the side-on overlap of the p orbitals, is
designated as a p bond.
Compounds Containing
Double Bonds
 The final result is a bond that looks like this.
Compounds Containing
Triple Bonds
 Ethyne or acetylene is the simplest triple
bond containing organic compound.
 Lewis Dot Formula for ethyne C2H2
 N = 2(8) + 2(2) = 20
 A = 2(4) + 2(1) =10
S = 10
Compounds Containing
Triple Bonds
 Lewis Dot Formula for ethyne C2H2

H ·· C ·· ·· ·· C ·· H or H C C H
Compounds Containing
Triple Bonds
 VSEPR
suggests C and H atoms are 180o apart.

H C C H
Compounds Containing
Triple Bonds
 Valence Bond Theory
sp hybrids for the C atoms
2 electrons remain in unhybridized p orbitals
Compounds Containing
Triple Bonds
 Valence Bond Theory
sp hybrids for the C atoms
2 electrons remain in unhybridized p orbitals
2s 2p two sp hybrids 2p
C  
Compounds Containing
Triple Bonds
C C
 triple bond results from head-on overlap
of two sp hybrid orbitals
Compounds Containing
Triple Bonds
 Note that this gives us one s bond and two p
bonds.
Compounds Containing
Triple Bonds
 The final result is a bond that looks like this.
Summary of Electronic &
Molecular Geometries
 Synthesis Question 1
 The basic shapes that we have discussed are present in
essentially all molecules. Shown below is the chemical
structure of vitamin B6 phosphate. What is the shape and
hybridization of each of the indicated atoms in vitamin B6
phosphate?
5

4
H O
O H2 C
O
P C OH
O
O
+
N CH 3
2
H
1
3
Synthesis Question 1
trigonal planar sp2 5

4 bent or angular sp3

H O
O H2 C
O
P C OH
O
O
+
N CH3

trigonal planar sp2 1 H

3 trigonal planar sp2

2 tetrahedral sp3
Group Question 1
 Shown below is the structure of penicillin-G.
What is the shape and hybridization of each of
the indicated atoms in penicillin-G?
5 6
3 4
2

H S CH 3
H O NH
H CH C C
CH 3
7
C C N CH
1 C CH 2 C
C OH
O
H C C O
H
H
9
8
10
Synthesis Question 2
 As we all know, in the wintertime we are more
likely to get shocked when we walk across carpet
and touch the door knob. Here is another
wintertime experiment to perform. Turn on a
water faucet until you have a continuous but
small stream of water coming from the faucet.
Brush your hair vigorously then hold the brush
near the stream of water. You will notice that the
stream bends towards the brush. Why does the
water bend?
Synthesis Question 2

 Since water is a highly polar molecule, it is

attracted by the electromagnetic field
generated by the hair brush. This causes
the stream to bend.
Group Question 2
 On a recent “infomercial” it was claimed
that placing a small horseshoe magnet
over the fuel intake line to your car’s
carburetor would increase fuel mileage
by 50%. The reason given for the
mileage increase was that “the magnet
aligned the molecules causing them to
burn more efficiently.” Will this work?
Should you buy this product?