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Figure 1 : 2-Ethenylpyrrole
2-Ethenylpyrrole
Electrophile
E = H at C5
E = H at C7
starting molecule
activated complex
E = NO2, products
2-Ethenylpyrrole
Electrophile
Ortho-NO2
Vinyl-NO2,
C7
starting molecule
activated complex
E = NO2, products
This was a singlet state calculation conducted using the computer software HyperChem v.8.04.
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.
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
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 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
Figure 13
Figure 14
Figure 15
Figure 16
INTERMEDIATES
Figure 17
Figure 18
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
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
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
-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
-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
E = H at C7
-24611
-24768
-24611
2-Ethenylpyrrole
Electrophile
starting molecule
activated complex
E = H, products
E = H at C5
-195669
-104754
-195669
E = H at C7
-195669
-105452
-195669
11
-24550
0
0,5
1,5
2,5
3,5
-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
-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
-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
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
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
-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
Vinyl-NO2, C7
-24611
-43829
-43739
2-Ethenylpyrrole
Electrophile
starting molecule
activated complex
E = NO2, products
Ortho-NO2
-195669
-191847
-183795
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
-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
-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
-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.
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