An Introduction to Frontier Molecular Orbital Theory-1

D. A. Evans, F. Michael

Stereoelectronic Effects

General Reviews
Fleming, I. Frontier Orbitals and Organic Chemical Reactions
Fukui, Acc. Chem. Res. 1971, 4, 57.

Geometrical constraints placed upon ground and transition states

by orbital overlap considerations.

Kirby, A. J. Stereoelectronic Effects.

Fukui Postulate for reactions:

Universal Effects Governing all Chemical Reactions

Steric Effects
Nonbonding interactions (van der Waals repulsion) between
substituents within a molecule or between reacting molecules
Me

Nu:

Chem 531

General Reaction Types

Me

SN2

Br

During the course of chemical reactions, the interaction of

the highest filled (HOMO) and lowest unfilled (antibonding)
molecular orbital (LUMO) in reacting species is very important
to the stabilization of the transition structure.

Nu

Br:

Radical Reactions (~10%):

A + B

A(:) + B(+)

O
R

Polar Reactions (~90%):

OOH

major

Lewis Base

R
O

minor

Nondirectional Electronic Effects (Inductive Effects):

Me
R

C
R

Br

SN1

+
R

Me

+ Br:

Lewis Acid

FMO concepts extend the donor-acceptor paradigm to non-obvious

families of reactions
Consider stabilization energy (E) when bringing atoms A & B
together:

rate decreases as R becomes more electronegative

E =

QAQB
R
Coulomb Term

2
mn

(cmAcnB)2
(Em - En)

Orbital Term

Fleming, page 27

Q: Charge density
: Dielectric constant
R: distance of A to B
c: coefficient of MO
m of species A, or
MO n of species B
: Overlap Integral
E: Energy of MO

The H2 Molecule (again!!)

Let's combine two hydrogen atoms to form the hydrogen molecule.
Mathematically, linear combinations of the 2 atomic 1s states create
two new orbitals, one is bonding, and one antibonding:

Linear Combination of Atomic Orbitals (LCAO): Orbital Coefficients

Each MO is constructed by taking a linear combination of the individual
atomic orbitals (AO):
Bonding MO

Rule one: A linear combination of n atomic states will create n MOs.

(antibonding)

Energy

1s

Antibonding MO

= C11 + C22
=C*11 C*22

The coefficients, C1 and C2, represent the contribution of each AO.

E
H

Chem 531

The H2 Molecular Orbitals

D. A. Evans, F. Michael

1s

H
2

E
(bonding)

Let's now add the two electrons to the new MO, one from each H atom:
(antibonding)

Rule Two: (C1)2 + (C2)2 = 1

The squares of the C-values are a measure of the electron population
in neighborhood of atoms in question
Rule Three: bonding(C1)2 + antibonding(C*1)2= 1
In LCAO method, both wave functions must each contribute
one net orbital
Consider the pi-bond of a C=O function: In the ground state pi-CO
is polarized toward oxygen. Note (Rule 2) that the antibonding MO
is polarized in the opposite direction.
C

H
1

1s

1s
E2

(antibonding)

H
2

(bonding)

Energy

Energy

E1

Note that E1 is greater than E2. Why?

C

(bonding)

Bonding Generalizations

D. A. Evans, F. Michael

Bond strengths (Bond dissociation energies) are composed of a

covalent contribution ( Ecov) and an ionic contribution ( Eionic).

Orbital orientation strongly affects the strength of the resulting bond.

For Bonds:

Bond Energy (BDE) = Ecovalent + Eionic

When one compares bond strengths between CC and CX, where X

is some other element such as O, N, F, Si, or S, keep in mind that
covalent and ionic contributions vary independently. Hence, the
mapping of trends is not a trivial exercise.

The following generalizations on covalent

bonding are useful.
Overlap between orbitals of comparable energy is more effective
than overlap between orbitals of differing energy.

better than

CC

Si

Better
than

For Bonds:

Better
than

This is a simple notion with very important consequences. It surfaces in

the delocalized bonding which occurs in the competing anti (favored)
syn (disfavored) E2 elimination reactions. Review this situation.

For example, consider elements in Group IV, Carbon and Silicon. We

know that C-C bonds are considerably stronger by Ca. 20 kcal mol-1
than C-Si bonds.
C

Chem 531

An anti orientation of filled and unfilled orbitals leads to better

overlap.
This is a corrollary to the preceding generalization.
There are two common situations.

Si

Case-1: Anti Nonbonding electron pair & CX bond

CSi

X
Si-SP3
C-SP3

C-SP3

C-SP3
CSi

H3CSiH3 BDE ~ 70 kcal/mol

Bond length = 1.87

CSi = 36 kcal/mol

SiSi = 23 kcal/mol

Weak bonds will have corresponding low-lying antibonds.

Formation of a weak bond will lead to a corresponding low-lying antibonding
orbital. Such structures are reactive as both nucleophiles & electrophiles

Better
than

lone pair
HOMO

* CX
LUMO

Case-2: Two anti sigma bonds

This trend is even more dramatic with pi-bonds:

CC = 65 kcal/mol

lone pair
HOMO

CC

H3CCH3 BDE = 88 kcal/mol

Bond length = 1.534

* CX
LUMO

X
A
Y

C
CY
HOMO

* CX
LUMO

Better
than

CY
HOMO

* CX
LUMO

D. A. Evans, F. Michael

Donor-Acceptor Properties of Bonding and Antibonding States

Donor Acceptor Properties of C-C & C-O Bonds

Consider the energy level diagrams for both bonding & antibonding
orbitals for C-C and C-O bonds.
* C-C

Chem 531

Hierarchy of Donor & Acceptor States

Following trends are made on the basis of comparing the bonding and
antibonding states for the molecule CH3-X where X = C, N, O, F, & H.
-bonding States: (CX)

* C-O

CH3CH3
CH3H

C-sp

C-sp

3
CH3NH2

O-sp3

CH3OH

decreasing -donor capacity

CH3F

C-C

poorest donor

C-O

The greater electronegativity of oxygen lowers both the bonding

& antibonding C-O states. Hence:
C-C is a better donor orbital than C-O

C-O

is a better acceptor orbital than

-anti-bonding States: (CX)

CH3H

C-C

CH3CH3
CH3NH2

Donor Acceptor Properties of Csp3-Csp3 & Csp3-Csp2 Bonds

* C-C
* C-C

C-sp3

better acceptor

C-sp3
C-sp2

CH3OH
CH3F

Increasing -acceptor capacity

best acceptor

The following are trends for the energy levels of nonbonding states
of several common molecules. Trend was established by
photoelectron spectroscopy.
Nonbonding States

C-C

better donor

C-C

The greater electronegativity of Csp2 lowers both the bonding &

antibonding CC states. Hence:
Csp3-Csp3 is a better donor orbital than Csp3-Csp2

Csp3-Csp2 is a better acceptor orbital than Csp3-Csp3

H3P:

H2S:

H3N:
H2O:

decreasing donor capacity

HCl:
poorest donor

Hybridization vs Electronegativity

D. A. Evans, F. Michael

Electrons in 2s states "see" a greater effective nuclear charge

than electrons in 2p states.

Chem 531

This correctly implies that the stability of nonbonding electron

pairs is directly proportional to the % of s-character in the doubly
occupied orbital
Least stable

This becomes apparent when the radial probability functions for s and
p-states are examined: The radial probability functions for the
hydrogen atom s & p states are shown below.

Csp3

Most stable

Csp2

Csp

The above trend indicates that the greater the % of s-character

at a given atom, the greater the electronegativity of that atom.
100 %

1s Orbital

2s Orbital

There is a linear relationship between %s character &

Pauling electronegativity

Radial Probabilit
y

Radial Probabilit
y

100 %

2s Orbital
2p Orbital

3s Orbital

3p Orbital

Electrons in s-states "see" a higher nuclear charge. This is even more

obvious in an electron density map (see
http://www.shef.ac.uk/chemistry/orbitron/). The s-orbitals have maximal
electron density at the nucleus, and the p-orbitals have none.

There is a direct relationship between %s character &

hydrocarbon acidity

Hyperconjugation: Carbocation Stabilization

D. A. Evans, F. Michael

The interaction of a vicinal bonding orbital with a p-orbital is referred

to as hyperconjugation.
This is a traditional vehicle for using valence bond to denote charge
delocalization.
+
+

R
C

R
H

Physical Evidence for Hyperconjugation

Bonds participating in the hyperconjugative interaction, e.g. CR,
will be lengthened while the C(+)C bond will be shortened.

Chem 531

First X-ray Structure of an Aliphatic Carbocation

The graphic illustrates the fact that the C-R bonding electrons can
"delocalize" to stabilize the electron deficient carbocationic center.

The Adamantane Reference

(MM2)

[F5SbFSbF5]

Note that the general rules of drawing resonance structures still hold:
the positions of all atoms must not be changed.

100.6

1.431

1.528

110

1.608

1.530

Me

Me

Me

Me

Stereoelectronic Requirement for Hyperconjugation:

coplanar orientation between interacting orbitals

Me

Me

T. Laube, Angew. Chem. Int. Ed. 1986, 25, 349

The Molecular Orbital Description

More substituted carbocations have more adjacent C-R bonds to

act as donors to the empty p orbital

CR

CR

Hence, more substituted carbocations are more stable.

+
C

CR

CR

+
+

H
H

bonding
interaction
H
H

Take a linear combination of CR and Csp2 p-orbital:

The new occupied bonding orbital is lower in energy. When you
stabilize the electrons in a system you stabilize the system itself.

+
+

H
H
H

least stable

1o

+
+

H
CH3
H

CH3
CH3

Me

+
+

H
H

2o

3o
most stable

"Negative" Hyperconjugation/Anomeric Effect

D. A. Evans, F. Michael

Delocalization of nonbonding electron pairs into vicinal antibonding

orbitals is also possible
R

zz

H
H

H
H

H
H

This delocalization is referred to as "negative" hyperconjugation

Since nonbonding electrons prefer hybrid orbitals rather than p

orbitals, this orbital can adopt either a syn or anti relationship to
the vicinal CR bond.

R:

zz

H
X

antibonding CR

Syn Orientation
R

Chem 531

X+

H
zz

filled
hybrid orbital

antibonding CR
R:

Anti Orientation
R

zz

R
X+

H
H

filled
X hybrid orbital
zz

The Molecular Orbital Description

Overlap between two orbitals is better in the anti orientation as
stated in "Bonding Generalizations" handout.

CR

Nonbonding e pair

X
zz

CR

As the antibonding CR orbital

decreases in energy, the magnitude
of this interaction will increase

The Expected Structural Perturbations

Change in Structure

Spectroscopic Probe

Shorter CX bond

X-ray crystallography

Longer CR bond

X-ray crystallography

Stronger CX bond

Infrared Spectroscopy

Weaker CR bond

Infrared Spectroscopy

Greater e-density at R

NMR Spectroscopy

Less e-density at X

NMR Spectroscopy

D. A. Evans, F. Michael

Infrared evidence for lone pair delocalization into

vicinal antibonding orbitals.
The NH stretching frequency of cis-methyl diazene is 200 cm-1 lower
than the trans isomer.
Me
H
H
Me
N
N
zz

Me

-1

filled
N-sp2

Me

zz

N
zz

zz

NH = 2188 cm

Chem 531

The Anomeric Effect and Related Issues

H
NH = 2317 cm -1

filled
N-sp2

..

antibonding
NH

antibonding
N NH
H

The low-frequency shift of the cis isomer is a result of NH bond

weakening due to the anti lone pair on the adjacent (vicinal)
nitrogen which is interacting with the NH antibonding orbital. Note
that the orbital overlap is not nearly as good from the trans isomer.
N. C. Craig & co-workers JACS 1979, 101, 2480.

Aldehyde CH Infrared Stretching Frequencies

The Anomeric Effect

It is not unexpected that the methoxyl substituent on a cyclohexane ring
prefers to adopt the equatorial conformation.
H
H

OMe

OMe
G = +0.8 kcal/mol
What is unexpected is that the closely related 2-methoxytetrahydropyran
prefers the axial conformation:
H
O

OMe
G = 0.6 kcal/mol

OMe

That effect which provides the stabilization of the axial OR conformer

which overrides the inherent steric bias of the substituent is referred to as
the anomeric effect.
Principal HOMO-LUMO interaction from each conformation is illustrated
below:
H
O

OMe

OMe
axial O lone pair CO
preferred
Since the antibonding CO orbital is a better acceptor orbital than the
antibonding CH bond, the axial OMe conformer is better stabilized by
zz
R
R
this interaction which is worth ca 1.2 kcal/mol.
R
O
Other electronegative substituents such as Cl, SR etc. also participate in
C
C
C
anomeric stabilization. H
zz
H
R
H
1.781
H
CH = 2730 cm -1
CH = 3050 cm -1
O
Cl H O O
Cl
We now conclude that this is another example of negative hyperconjugation.
This conformer
1.819 Cl
The IR CH stretching frequency for aldehydes is lower than the
closely related olefin CH stretching frequency. For years this
observation has gone unexplained.

axial O lone pair CH

preferred by 1.8 kcal/mol

Why is axial CCl bond longer ?