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Molecular Geometry and Bonding Theories

Two Simple Theories of Covalent Bonding

Valence Shell Electron Pair Repulsion Theory


VSEPR R.

J. Gillespie - 1950s

Valence Bond Theory


Hybridized

orbitals L. Pauling - 1930s & 40s

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

2
3

lone pair to lone pair repulsion is strongest lone pair to bonding pair repulsion is intermediate 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 Formulas 1s 2s 2p Be 3s 3p Cl [Ne]

Lewis
Be . Cl

Hybrid Orbitals

Dot Formula
Cl Be Cl

Electronic Geometry
Cl Be Cl 180o - linear

Hybrid Orbitals

VSEPR

Polarity
Cl - Be - Cl Electroneg ativities 3.5 1.5 3.5
2.0 2.0

Cl Be Cl
180o-linear

very polar bonds

Hybrid Orbitals

VSEPR

Polarity
Cl - - - Be - - - Cl

Cl Be Cl
180o-linear

bond dipoles are symmetric 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 Formulas 1s 2s 2p B 3s 3p Cl [Ne]

Lewis
B.

. Cl

Hybrid Orbitals

Dot Formula
Cl B Cl Cl

Electronic Geometry

120-trigonal planar

Hybrid Orbitals

VSEPR
Cl Cl

Polarity
B - Cl Electroneg ativities 1.5 3.0
1.5

Cl 120-trigonal planar

v ery polar bonds

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

C [He]

2s

2p

.. .C .

Hybrid Orbitals

Electronic Structures

Lewis Formulas

C [He] H

2s 1s

2p

.. .C . H.

Hybrid Orbitals

Dot Formula

Electronic Geometry

..

H .. . . .H H.C .. H

. .

C ..

. .

tetrahedral 109.5o bond angles

Hybrid Orbitals

VSEPR H
H C H H

Polarity
C - H Electroneg ativities 2.5 2.1
0.4

tetrahedral

slightly polar bonds

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

As [Ar] 3d10 2s F [He]

4s

4p

2p

. As . . F .

Hybrid Orbitals

Dot Formula
F F As F

Electronic Geometry
As trigonal bipyramidal

F F

Hybrid Orbitals

VSEPR
F F F As F F

Polarity
As - F Electroneg ativities 2.1 4.0
1.9

very polar bonds

trigonal bipyramid

Hybrid Orbitals

VSEPR
F F F As F F

Polarity
F F F As F F
symmetric dipoles cancel nonpolar molecule

trigonal bipyramid

Hybrid Orbitals

Molecular Geometry

Hybrid Orbitals

Valence Bond (Hybridization)


4p 4d ___ ___ ___ ___ ___ five sp3 d hybrids 4s

As [Ar] 3d10

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
. Se . F.

4s 4p Se [Ar] 3d10 2s 2p F [He]

Hybrid Orbitals

Dot Formula
F F F Se F F F

Electronic Geometry
Se octahedral

Hybrid Orbitals

VSEPR
F F F F Se F F octahedral

Polarity
Se - F Electroneg ativities 2.4 4.0
1.6

v ery polar bonds

Hybrid Orbitals

VSEPR
F F F F Se F F octahedral

Polarity
F F F F Se F F
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 C C H H

H or H C C

H H

Compounds Containing Double Bonds

VSEPR
suggests C atoms at center of two equilateral triangles
H
C C

Compounds Containing Double Bonds

Valence Bond Theory


sp2 hybrids for the C atoms 1 electron remains in an unhybridized p orbital

2s C

2p

three sp2 hybrids 2p

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.

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

Compounds Containing Triple Bonds

triple bond results from head-on overlap of two sp hybrid orbitals

C C

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 OH N H
+

H O O O P O 2 1 3 H2 C

CH 3

Synthesis Question 1
trigonal planar sp2 5 4 bent or angular sp3 OH N trigonal planar sp2 1 H 3 trigonal planar sp2 2 tetrahedral sp3
+

H O O O P O H2 C

CH3

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 3 2 CH 3 S H NH H O C CH C H CH 3 C N CH C C C CH 2 OH C O H O C C H H 9 8 10 4 6

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 cars 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?