Spartan: Conjugated Systems

1.
Build, energy minimize, and perform 6-31G* Equilibrium Geometry
calculations for 1,3-pentadiene (both geometries) and 1,4-pentadiene. Compare the
relative energy for each compound in kJ/mol.
a. 1,3E pentadiene (s-cis geometry)
b. 1,3E pentadiene (s-trans geometry)

(Note that the s-cis and

s-trans geometries are
the same molecule in
different conformations.)

c. 1,4-pentadiene

d. Find the bond length for the C2-C3 bond in s-cis and s-trans-1,3E-pentadiene.
Find the bond length for the C2-C3 bond in 1,4-pentadiene. Are the bond lengths
different? Why?
e. Which pentadiene is most stable? Why?
2. Build 1,3-butadiene, and calculate an Energy Profile for rotation around the C2C3 bond using the following method:
After building the molecule in the s-cis geometry, select Constrain Dihedral
from the Geometry menu and click the four carbons in sequence. Click the little
pink lock in the lower right-hand side of the screen. Make sure that the constraint
is selected (the constraint is the pink bridge that is now in your molecule; if it is not
selected, and you cannot select it, make sure that Constrain Dihedral is still
selected in the Geometry menu). If the dihedral angle is close to 180, click the
pink lock to unlock the constraint, return to the Build mode, select the bond, and
Alt-left-drag to rotate the angle to close to 0, and then constrain the dihedral as
before. In the Properties dialog, select Dynamic, and set the range and the
number of steps. A useful range is 0 to 350, with 36 steps, which should allow
generation of conformers every 10. In the Calculations dialog, select Energy
Profile (instead of Equilibrium Geometry). Submit the calculations using HartreeFock 6-31G*. Spartan will create a new file with Prof.M001 after the name you
gave. When the calculations complete, Spartan should ask to open the new file.
Select OK, and close the original file.
a. What dihedral angle do you predict should be most stable? Why?
b. Select Measure Dihedral in the Geometry menu, and click on the four
carbons in sequence. Click the small P at the bottom right of the screen. Select
Spreadsheet in the Display menu. Click Add, and select Rel. E. and set the
units to kJ/mol. Select Plots from the Display menu, and set the x-axis to
Dihedral and the y-axis to Rel. E.
According to the Spartan calculations, what is the most stable dihedral angle? Is
this angle more stable than a more staggered conformation? Is this what you
expected? Explain why the geometries that yield energy minima are the minimum
energy geometries.
c. Open the Surfaces dialog from the Setup menu, and add LUMO, HOMO,
HOMO (-1), and HOMO (-2). Change the calculation type to Energy in the

Calculations dialog, and click Submit. (The calculations may take a little while.)
Look at the various molecular orbital surfaces while allowing the molecule to rotate
around the C2-C3 bond.
Does the information from the MO surfaces help you to rationalize the energy
minima in the Energy versus Dihedral angle plot? Explain your rationalization.
d. Pick a stable conformation, show the MOs in order of increasing energy, and
explain why this is a useful representation.
3. Build, energy minimize, and perform 6-31G* Equilibrium Geometry
calculations for the carbocation that would form following the loss of a leaving group
from the 3 or the 4 position of a 1-pentene derivative (e.g., from 3-bromo-1-pentene
or 4-bromo-1-pentene). Compare the relative energies of the two secondary
carbocations. Which carbocation intermediate is more stable? Why?
Add the HOMO surface to both molecules. Does the shape of the HOMO surface
support or contradict your explanation? Why?
4. Build, energy minimize, and perform 6-31G* Equilibrium Geometry
calculations for aniline, benzene, and nitrobenzene. Open the Properties dialog in
the Display menu. Click on the different carbon atoms in each compound, and
record the Natural charge.
For each molecule, predict which carbon atom(s) should be most susceptible to
attack by an electrophile, and justify your answers (note that the justification
should be more profound than Spartan says so!).
5. Build, energy minimize, and perform 6-31G* Equilibrium Geometry
calculations for the molecules below. Upon completion of the calculations, close all of
the files except one, and then Append (in the File menu) the other molecule files to
the open file. Select Spreadsheet in the Display menu, and add Rel. E. (kJ/mol)
to the spreadsheet. In a table in your report summarize the relative energies.
Explain the observed differences in energy between the molecules.

p-diethylbenzene

deca-5-yne-1,9-diene

diethylprismane

(2E,8E)-deca-5-yne-2,8-diene

(2E,4E,6E,8E)-2,4,6,8-decatetraene

(3E,7E)-deca-5-yne-3,7-diene

deca-5-yne-1,2-diene

6. Build, energy minimize, and perform 6-31G* Equilibrium Geometry

calculations for the molecules below. Upon completion of the calculations, close all of
the files except one, and then Append (in the File menu) the other molecule files to
the open file. Select Spreadsheet in the Display menu, and add Rel. E. (kJ/mol)
to the spreadsheet. In a table in your report summarize the relative energies.
Explain the observed differences in energy between the molecules.