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Exercise 27

HyperChem 8.04 AM1 Calculations.


Electrophilic Aromatic Substitution of Monosubstituted Benzenes. Hammond Postulate
Theoretical Organic Chemistry, 2013
Anastazija Ristovska
2-Ethenyl pyrrole is a monosubstituted pyrrole molecule with an electron-donating alkyl ethenyl
group attached to its ortho position. For this reason, 2-ethenyl pyrrole is more reactive than pyrrole, with
activated meta and ortho positions (or more precis4ely, positions 3 and 5, but not necessarily position 4),
susceptible to a reaction with an electrophile. Were going to check the energies of the intermediates of
the nitration reaction of 2-ethenyl pyrrole, as well as the energies of the three possible final products of
mononitration. The goal is to fill out the tables shown below and plot the data.

Figure 1 : 2-Ethenylpyrrole

2-Ethenylpyrrole
Electrophile

E = H at C5

AM1 Energy (kcal/mol)


E = H at C4
E = H at C3
E = H at C6

E = H at C7

starting molecule
activated complex
E = NO2, products

2-Ethenylpyrrole
Electrophile

Ortho-NO2

AM1 Energy (kcal/mol)


Vinyl-NO2,
Meta-NO2, C4 Meta-NO2, C3
C6

Vinyl-NO2,
C7

starting molecule
activated complex
E = NO2, products

Figure 2: Cation Intermediate, +1 charge on C5, electrophile


substituent (H+) on C4

Figure 3: HOMO Plot of the Cation Intermediate shown left

The positive charge of this cation of 2-ethenylpyrrole rests on the


5C carbon atom of the pyrrole ring, whereas the electrophilic
substituent which is a proton in this case binds to the 4C carbon
atom of the pyrrole ring. The HOMO energy of this molecule is 13.034eV, and its LUMO energy is -5.291eV. The difference in
energies between the LUMO and HOMO orbitals is 7.743eV. The
molecular symmetry point group is C1. The total energy of the
system is -24832kcal/mol, the total charge on the system is +1, the
electronic energy is -103729kcal/mol, and the heat of formation is
209.88kcal/mol. There are a total of 36 electrons and 36 orbitals,
with 18 double occupied levels. The core-core interaction energy is
78897kcal/mol. If we add the electronic energy calculated through
solving the Schrdinger equation to the core-core interactions
energy we will obtain the total energy of the system. As also stated
in the previous assignment, the total energy E of the molecule
determines the structure and stability of the molecule, and it represents the sum of the kinetic energies of
all the particles forming the molecules plus the sum of all the potential energies of all the interactions of
the particles forming the molecule. In particular, it is a sum of the kinetic energies of all nuclei, plus the
sum of the potential energy of all Coulomb interactions between nuclei, plus the sum of the potential
energies of all Coulomb interactions between nuclei and electrons, plus the sum of the potential energies
of all Coulomb interactions between electrons. This definition can be simplified by applying the BornOppenheimer approximation according to which the nuclei are assumed to be stationary, i.e. their kinetic
energies are zero, and they are simply point charges, implying that the potential energy of all Coulomb
interactions between nuclei is in fact Coulomb repulsion between point charges.

Figure 4: MO Energy Levels for the Cation


Intermediate shown on top

This was a singlet state calculation conducted using the computer software HyperChem v.8.04.

Figure 7: Cation Intermediate with +1 Charge on C4, electrophile


substituent on C5

Figure 6: HOMO Plot of the Cation in Figure 6

The positive charge of this cation of 2-ethenylpyrrole rests on the


4C carbon atom of the pyrrole ring, whereas the electrophilic
substituent which is a proton in this case binds to the 5C carbon
atom of the pyrrole ring. The HOMO energy of this molecule is 14.930eV, and its LUMO energy is -5.935eV. The difference in
energies between the LUMO and HOMO orbitals is 8.995eV.
The molecular symmetry point group is CS. The total energy of
the system is -24729kcal/mol, the total charge on the system is
+1, the electronic energy is -104754kcal/mol, and the heat of
formation is 213.08kcal/mol. There are a total of 36 electrons and
36 orbitals, with 18 double occupied levels. The core-core
interaction energy is 80035kcal/mol.
Figure 5: Energy Levels for the Cation
Intermediate shown on top

Figure 8: right: Cation Intermediate with +1 Charge on C2, electrophile substituent on C3; left: HOMO Plot of Cation;
the purple (or pink in other plots) orbitals are anti-bonding, the green ones represent the bonding MOs.

The positive charge of this cation of 2-ethenylpyrrole rests on the


2C carbon atom, whereas the electrophilic substituent which is a
proton in this case binds to the 3C carbon atom of the pyrrole ring.
The HOMO energy of this molecule is -14.114eV, and its LUMO
energy is -6.144eV. The difference in energies between the LUMO
and HOMO orbitals is 7.970eV. The molecular symmetry point
group is C1. The total energy of the system is -24823kcal/mol, the
total charge on the system is +1, the electronic energy is 104046kcal/mol, and the heat of formation is 219.09kcal/mol.
There are a total of 36 electrons and 36 orbitals, with 18 double
occupied levels. The core-core interaction energy is 79223kcal/mol.
Figure 9: Energy Levels for the Cation
Intermediate shown in figure on top

Figure 10: Cation Intermediate with +1 Charge on C6, electrophile substituent on C7 (C6 and C7 constitute the vinyl
i.e. ethenyl group); the HOMO plot is superimposed on the cation structural formula

The HOMO energy is -14.743eV, and its LUMO energy is 6.716eV. The difference in energies between the LUMO and
HOMO orbitals is 8.027eV. The molecular symmetry point group
is C1. The total energy of the system is -24768kcal/mol, the
electronic energy is -105452kcal/mol, and the heat of formation is
273.67kcal/mol. The core-core interaction energy is
80683kcal/mol.

Figure 11

The HOMO energy is -13.049eV, and its LUMO energy is -8.134eV.


The difference in energies between the LUMO and HOMO orbitals is
4.915eV. The molecular symmetry point group is C1. The total energy
of the system is -24728kcal/mol, the electronic energy is 106091kcal/mol, and the heat of formation is 303.81kcal/mol. The
core-core interaction energy is 81363kcal/mol.

Figure 12

Figure 13

The HOMO energy of ortho-nitrated 2-ethenylpyrrole is -9.468eV, and its LUMO energy is -1.736eV.
The difference in energies between the LUMO and HOMO orbitals is 7.750eV. The molecular symmetry
point group is CS. The total energy of the system is -43777kcal/mol, the electronic energy is
-183795kcal/mol, and the heat of formation is 159.63kcal/mol. There are a total of 52 electrons, 46
orbitals, and 26 double occupied levels. This is a singlet state system.

The HOMO energy of meta-nitrated 2ethenylpyrrole at the C4 position is -9.459eV;


its LUMO energy is -1.209eV. The difference
in energies between LUMO and HOMO is
8.250eV. The molecular symmetry point
group is CS. The total energy of the system is 43734kcal/mol, the electronic energy is 187680kcal/mol, and the heat of formation is
157.37kcal/mol. The core-core interaction
energy is 143946cal/mol. There are a total of
52 electrons, 46 orbitals, and 26 double
occupied levels. This is a singlet state system.
Figure 14

The HOMO energy of meta-nitrated 2ethenylpyrrole at position 3 of the ring is 9.340eV; its LUMO energy is -1.396eV. The
difference in energies between LUMO and
HOMO is 7.944eV. The molecular symmetry
point group is C1. The total energy of the system
is -43721kcal/mol, the electronic energy is 192578kcal/mol, and the heat of formation is
170.25kcal/mol. The core-core interaction energy
is 148858cal/mol. There are a total of 52
electrons, 46 orbitals, and 26 double occupied
levels. This is a singlet state system.
Figure 15

The HOMO energy of vinyl-nitrated 2ethenylpyrrole at position 1 of the ethenyl group is


-9.226eV; its LUMO energy is -1.886eV. The
difference in energies between LUMO and
HOMO is 7.340eV. The molecular symmetry
point group is C1. The total energy of the system
is -43724kcal/mol, the electronic energy is 191957kcal/mol, and the heat of formation is
167.31kcal/mol. The core-core interaction energy
is 148234cal/mol. There are a total of 52
electrons, 46 orbitals, and 26 double occupied
Figure 16

levels. This is a singlet state system.

Figure 13

The HOMO energy of vinyl-nitrated 2ethenylpyrrole at position 2 of the ethenyl


group as displayed in the figure on left is 9.548eV; its LUMO energy is -1.927eV. The
difference in energies between LUMO and
HOMO is 7.621eV. The molecular symmetry
point group is CS. The total energy of the
system is -43739kcal/mol, the electronic energy
is -183212kcal/mol, and the heat of formation
is 152.69kcal/mol. The core-core interaction
energy is 139473cal/mol. There are a total of
52 electrons, 46 orbitals, and 26 double
occupied levels. This is a singlet state system.

Figure 14

Figure 15

Figure 16

INTERMEDIATES

Figure 17

The HOMO energy of the activated complex intermediate of


the ortho nitration 2-ethenylpyrrole at position 5 of the pyrrole
ring as displayed in the figure above is -14.817eV; its LUMO
energy is -7.335eV. The difference in energies between LUMO
and HOMO is 7.482eV. The molecular symmetry point group is
C1. The total energy of the system is -43854kcal/mol, the
electronic energy is -191847kcal/mol, and the heat of formation
is 351.82kcal/mol. There are a total of 52 electrons, 47 orbitals,
and 26 double occupied levels. This is a singlet state system.
The total charge on the system is +1, mostly located on position
4 of the pyrrole ring.

Figure 18

The HOMO energy of the activated complex


intermediate of the meta nitration 2-ethenylpyrrole at
position 4 of the pyrrole ring as displayed in the figure on
left is -13.798eV; its LUMO energy is -7.467eV. The
difference in energies between LUMO and HOMO is
6.331eV. The molecular symmetry point group is C1. The
total energy of the system is -43855kcal/mol, the
electronic energy is -189771kcal/mol, and the heat of
formation is 350.88kcal/mol. The core-core interaction
energy is 145916kcal/mol. There are a total of 52
electrons, 47 orbitals, and 26 double occupied levels. This
is a singlet state system. The total charge on the system is
+1, i.e. it is a cation intermediate, with the positive charge
mostly located on position 5 of the pyrrole ring.

The HOMO energy of the activated complex


intermediate of the meta nitration 2-ethenylpyrrole at
position 3 of the pyrrole ring as displayed in the figure
on left is -14.745eV; its LUMO energy is -7.330eV.
The difference in energies between LUMO and
HOMO is 7.415eV. The molecular symmetry point
group is C1. The total energy of the system is 43877kcal/mol, the electronic energy is 195812kcal/mol, and the heat of formation is
329.18kcal/mol. The core-core interaction energy is
151935kcal/mol. There are a total of 52 electrons, 47
orbitals, and 26 double occupied levels. This is a
singlet state system. The total charge on the system is
Figure 19

+1, i.e. it is a cation intermediate, with the positive


charge mostly located on position 2 of the pyrrole ring.

Figure 20

The HOMO energy of the activated complex intermediate of the vinyl nitration 2-ethenylpyrrole at
position 2 of the vinyl group as displayed in the figure on top is -14.826eV; its LUMO energy is -7.514eV.
The difference in energies between LUMO and HOMO is 7.312eV. The molecular symmetry point group
is C1. The total energy of the system is -43829kcal/mol, the electronic energy is -188973kcal/mol, and
the heat of formation is 377.66kcal/mol. The core-core interaction energy is 145144kcal/mol. There are a
total of 52 electrons, 47 orbitals, and 26 double occupied levels. This is a singlet state system. The total
charge on the system is +1, i.e. it is a cation intermediate, with the positive charge mostly located on
position 1 of the ethenyl group.

Figure 19

The HOMO energy of the activated complex intermediate of the vinyl nitration 2-ethenylpyrrole at
position 1 of the vinyl group as displayed in the figure on top is -14.034eV; its LUMO energy is -8.609eV.
The difference in energies between LUMO and HOMO is 5.425eV. The molecular symmetry point group
is C1. The total energy of the system is -43789kcal/mol, the electronic energy is -195669kcal/mol, and
the heat of formation is 417.42kcal/mol. The core-core interaction energy is 151880kcal/mol. There are a
total of 52 electrons, 47 orbitals, and 26 double occupied levels. This is a singlet state system. The total
charge on the system is +1, i.e. it is a cation intermediate, with the positive charge mostly located on
position 2 of the ethenyl group.
The neutral molecule in its ground state, with total charge on the system of 0, and spin multiplicity of 1,
has an energy of its highest occupied molecular orbital (HOMO) of -8.340 eV, and an energy of its lowest
unoccupied molecular orbital (LUMO) of 0.584 eV. The difference between the energies of the LUMO
and HOMO orbitals is [LUMO] [HOMO] = 0.584 - (-8.340) = 8.924 eV. The total energy is -24611
kcal/mol. The electronic energy of ground-state 2-ethenylpyrrole is -103279 kcal/mol. The heat of
formation is 166.47 kcal/mol.

10

Electrophile E=H
2-Ethenylpyrrole
AM1 Energy
Total Energy
kcal/mol
Electronic Energy
kcal/mol
Heat of Formation
kcal/mol
HOMO Energy eV
LUMO Energy eV
LUMO-HOMO eV

Position 5 of Pyrrole Ring


starting
activated
final
molecule
complex
products

Electrophile E=H
2-Ethenylpyrrole
AM1 Energy
Total Energy
kcal/mol
Electronic Energy
kcal/mol
Heat of Formation
kcal/mol
HOMO Energy eV
LUMO Energy eV
LUMO-HOMO eV

Position 3 of Pyrrole Ring


starting
activated
final
molecule
complex
products

Electrophile E=H
2-Ethenylpyrrole
AM1 Energy
Total Energy
kcal/mol
Electronic Energy
kcal/mol
Heat of Formation
kcal/mol
HOMO Energy eV
LUMO Energy eV
LUMO-HOMO eV

Position 2 of Vinyl Branch


starting
activated
final
molecule
complex
products

Position 4 of Pyrrole Ring


starting
activated
final
molecule
complex
products

-24611

-24729

-24611

-24611

-24832

-24611

-195669

-104754

-195669

-195669

-103729

-195669

417.42

213.08

417.42

417.42

209.88

417.42

-8.340
0.584
8.924

-14.930
-5.935
8.995

-8.340
0.584
8.924

-8.340
0.584
8.924

-13.034
-5.291
7.743

-8.340
0.584
8.924

Position 1 of Vinyl Branch


starting
activated
final
molecule
complex
products

-24611

-24823

-24611

-24611

-24728

-24611

-195669

-104046

-195669

-195669

-106091

-195669

417.42

219.09

417.42

417.42

303.81

417.42

-8.340
0.584
8.924

-14.114
-6.144
7.970

-8.340
0.584
8.924

-8.340
0.584
8.924

-13.049
-8.134
4.915

-8.340
0.584
8.924

-24611

-24768

-24611

-195669

-105452

-195669

417.42

273.67

417.42

-8.340
0.584
8.924

-14.743
-6.716
8.027

-8.340
0.584
8.924

2-Ethenylpyrrole
Electrophile
starting molecule
activated complex
E = H, products

E = H at C5
-24611
-24729
-24611

AM1 Total Energy (kcal/mol)


E = H at C4
E = H at C3
E = H at C6
-24611
-24611
-24611
-24832
-24823
-24728
-24611
-24611
-24611

E = H at C7
-24611
-24768
-24611

2-Ethenylpyrrole
Electrophile
starting molecule
activated complex
E = H, products

E = H at C5
-195669
-104754
-195669

AM1 Electronic Energy (kcal/mol)


E = H at C4
E = H at C3
E = H at C6
-195669
-195669
-195669
-103729
-104046
-106091
-195669
-195669
-195669

E = H at C7
-195669
-105452
-195669

11

-24550
0

0,5

1,5

2,5

3,5

Total Energy (kcal/mol)

-24600

-24650

-24700

-24750

E = H at C5
E = H at C4

-24800

E = H at C3
E = H at C6
E = H at C7

-24850

Electronic Energy (kcal/mol)

-116500

-126500

E = H at C5
E = H at C4
E = H at C3
E = H at C6
E = H at C7

-136500
-146500

-156500
-166500
-176500

-186500
-196500

Reaction Coordinate

Electronic Energy (kcal/mol)

-106500

Reaction Coordinate

E = H at C5
E = H at C4
E = H at C3
E = H at C6
E = H at C7
Reaction Coordinate

12

Electrophile E=
NO2
2-Ethenylpyrrole
AM1 Energy
Total Energy
kcal/mol
Electronic Energy
kcal/mol
Heat of Formation
kcal/mol
HOMO Energy eV
LUMO Energy eV
LUMO-HOMO eV

Position 5 of Pyrrole Ring

Position 4 of Pyrrole Ring

starting
molecule

activated
complex

final
products

starting
molecule

activated
complex

final
products

-24611

-43854

-43777

-24611

-43855

-43734

-195669

-191847

-183795

-195669

-189771

-187680

417.42

351.82

113.94

417.42

350.88

157.37

-8.340
0.584
8.924

-14.817
-7.335
7.482

-9.486
-1.736
7.750

-8.340
0.584
8.924

-13.798
-7.467
6.331

-9.459
-1.209
8.250

Electrophile E=H
2-Ethenylpyrrole
AM1 Energy
Total Energy
kcal/mol
Electronic Energy
kcal/mol
Heat of Formation
kcal/mol
HOMO Energy eV
LUMO Energy eV
LUMO-HOMO eV

Position 3 of Pyrrole Ring


starting
activated
final
molecule
complex
products

Electrophile E=H
2-Ethenylpyrrole
AM1 Energy
Total Energy
kcal/mol
Electronic Energy
kcal/mol
Heat of Formation
kcal/mol
HOMO Energy eV
LUMO Energy eV
LUMO-HOMO eV

Position 2 of Vinyl Branch


starting
activated
final
molecule
complex
products

Position 1 of Vinyl Branch


starting
activated
final
molecule
complex
products

-24611

-43877

-43721

-24611

-43789

-43724

-195669

-195812

-192578

-195669

-195669

-191957

417.42

329.18

170.25

417.42

417.42

167.31

-8.340
0.584
8.924

-14.745
-7.330
7.415

-9.340
-1.396
7.944

-8.340
0.584
8.924

-14.034
-8.609
5.425

-9.226
-1.886
7.340

-24611

-43829

-43739

-195669

-188973

-183212

417.42

377.66

152.69

-8.340
0.584
8.924

-14.826
-7.514
7.312

-9.548
-1.927
7.621

2-Ethenylpyrrole
Electrophile
starting molecule
activated complex
E = NO2, products

Ortho-NO2
-24611
-43854
-43777

Meta-NO2, C4
-24611
-43855
-43734

AM1 Energy (kcal/mol)


Meta-NO2, C3
Vinyl-NO2, C6
-24611
-24611
-43877
-43789
-43721
-43724

Vinyl-NO2, C7
-24611
-43829
-43739

2-Ethenylpyrrole
Electrophile
starting molecule
activated complex
E = NO2, products

Ortho-NO2
-195669
-191847
-183795

AM1 Electronic Energy (kcal/mol)


Meta-NO2, C4
Meta-NO2, C3
Vinyl-NO2, C6
-195669
-195669
-195669
-189771
-195812
-195669
-187680
-192578
-191957

Vinyl-NO2, C7
-195669
-188973
-183212

13

In the plot below, the starting molecule energy was high compared to the activated complex and final product
energies (-24611 kcal/mol which is very high compared to the range of intermediates and products, -43877 to 43721 kcal/mol), thus we could not display to scale its energy as a data point on the plot, although it can be zoomed
out in the corresponding excel document for this exercise.
-43670
1,6

2,1

2,6

3,1

Meta-NO2, C4
Ortho-NO2
Meta-NO2, C3
Vinyl-NO2, C6

Total Energy (kcal/mol)

-43720

Vinyl-NO2, C7

-43721

-43724,
final product
energy
-43734
-43739

-43770
-43777
-43789,
activated
complex
energy

-43820
-43829

-43855

-43854

-43870
-43877

-43920

Reaction Coordinate

14

Electronic Energy (kcal/mol)

-182000
-184000
-186000
Ortho-NO2

-188000

Meta-NO2, C4

-190000

Meta-NO2, C3

-192000

Vinyl-NO2, C6

-194000

Vinyl-NO2, C7

-196000
-198000

Reaction Coordinate

-178000

-180000

-182000

Electronic Energy (kcal/mol)

-184000

-186000
Ortho-NO2
Meta-NO2, C4

-188000

Meta-NO2, C3
Vinyl-NO2, C6

-190000

Vinyl-NO2, C7

-192000

-194000

-196000

-198000

Reaction Coordinate

15

Appendix
Given are the structural formulas with atom numbering for reference to the HyperChem 8.04 output files
containing detailed info of the molecular semi-empirical calculations for select molecules. The numbering
of the atoms as displayed by the software on screen for the given calculation is crucial for interpreting the
data output file. Given are also the plots of HOMO of select molecules.

16

17

18

19

20

21

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