Problem Set #2

1. Construct a MO diagram for the following molecules. Please explain explicitly any assumptions that you
made. Please draw the shapes of the frontier molecular orbitals (both HOMO and LUMO).
(a) N2
(b) CO
(c) FCH3
(d) H2C=O
(e) HCCH
(f) H2C=CH2
2. Construct a MO diagram for the -system of the following molecules. Please explain explicitly any
assumptions that you made. Please draw the shapes of the frontier molecular orbitals (both HOMO and
LUMO).
(a)

(b)

(c)

(d)

O
H

3. In the Hckel MO treatment, orbitals on nonadjacent atoms are assumed to have no interaction. The
concept of homoconjugation suggests that such orbitals may interact, especially in rigid structures in which
the orbitals are directed toward one another.
Consider norbornadiene:

a. Construct an MO diagram of the -system according to Hckel MO theory and rank the orbital energies.
b. Construct the qualitative MO diagram that would result from significant overlap between the C(3) and
C(5) and C(2) and C(6) orbitals.
4. Diazabicyclooctane 1 is a stronger base than the monoaza-derivative 2.
explain.

Please use FMO theory to

N
N

5. Predict the preferred site of protonation for each of the following molecules and explain the basis of your
prediction.
(a)
N
Ph

Ph
H

(b)
H3C

(c)

O
NH2

(d)
N
H

NH2

6.

It has been determined computationally that carboxylate ions are more basic between the oxygens
between the alkyl group and an oxygen (for references, see: Gandour, R. D. J. Am. Chem. Soc. 1990,
112, 7816). In qualitative terms, the two lone pairs on the oxygen of the carboxylate can be considered to
have different basicities. Rationalize the different using Frontier Molecular Orbital theory.
Less basic

More basic
O
R

7. Analyze the interaction between a filled p-orbital of a carbanion on an unshared electron pair on nitrogen.
Assume sp3 hybridization for nitrogen and the conformation in which the unshared electron pair has
maximum overlap with the carbon p-orbital.
8. Using molecular orbital diagrams of the -system, explain the stability of each cyclic leaving group.
(a)
R

Ph

Pd(PPh3)4 (5 mol %)

Me
+

EtO2C

CO2Et

NaH, THF, reflux

70%

EtO2C
EtO2C

Ph
Me

leaving group

Fisher, E. L.; Lambert, T. H. Org. Lett. 2009, 11, 4108.

(b)
Cl
Ph

Cl

Cl

Cl
Ph

Ph

OH

Cl
+

Ph

Ph

Me

Ph

Me

Ph

Ph

leaving group

Kelly, B. D.; Lambert, T. H. J. Am. Chem. Soc. 2009, 131, 13930.

(c) Can these groups be used interchangeably?

cf.

Cl

Ph

Ph

Pd(PPh3)4 (5 mol %)

Me
+

EtO2C

CO2Et

NaH, THF, reflux

????

Ph

Use molecular orbital diagrams to explain why or why not.

9. Please provide complete, detailed mechanisms for the following reactions. Watch formal charges and show
the flow of electrons for every single step!
(a)

(b)
N

Br

H
N

CF3CO2H

Br2
CCl4

Br

(c)

(d)
Me

Me

Me

Me

Me

Me

Me

HCl (cat.)
CH2Cl2

Br

O
Br

Br

(e)

CN
O

NaH
THF
H

O
O

CN

(f)
O

Me

1. EtONa

O
OEt

2.

Br

Br

CO2Et

CN

Me

SO2Ph

1. EtONa

PhO2S

2. H3O+
(work up)

NH
O