Exercise 6: Alternant Odd and Even and Non-Alternant Hydrocarbons

Theoretical Organic Chemistry, 2013

Anastazija Ristovska

Figure 1 Hydrocarbon

This molecule is an even alternant hydrocarbon, since the number of starred carbon atoms equals the
number of non-starred carbon atoms, i.e. it has an even number of atoms.

Figure 2 Triphenylmethyl Radical, drawn using HyperChem8

Triphenylmethyl radical has 10 non-starred and 9 starred carbon atoms; furthermore it has a total of 19
carbon atoms, which is an odd number. It can be seen from the figure that the system is alternant. That
makes triphenylmethyl radical an odd alternant system.
The number of pi electrons is 19.
We determine the energy levels of the radical using the Huckel-C program.
1

Figure 3 HMO Energy Levels for Triphenylmethyl Radical

MO Energy
E19
E18
E17
E16
E15
E14
E13
E12
E11
E10
E9
E8
E7
E6
E5
E4
E3
E2
E1

-2,394
-2
-2
-1,506
-1
-1
-1
-1
-1
0
1
1
1
1
1
1,506
2
2
2,394

E19=
E18=
E17=
E16=
E15=
E14=
E13=
E12=
E11=
E10=
E9=
E8=
E7=
E6=
E5=
E4=
E3=
E2=
E1=

+2,394
+2
+2
+1,506
+
+
+
+
+

-
-
-
-
-
-1,506
-2
-2
-2,394

As can be seen from the diagram, there is one pair of electron in each molecular orbital ranging from
MO1 to MO9, and there is only 1 unpaired electron in MO10. MO10 has exactly 0 beta energy. Odd
alternant systems in general contain energy levels with zero energy. Benzyl radical is one example, and
triphenylmethyl radical is another. The electron densities of all atoms of triphenylmethyl radical are unity.
The Huckel matrix was constructed as follows:

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19

1
0
1

2
1
0
1

3
1
0
1

4
1
0
1

1
0
1

6
1

1
0
1

1
0
1

1
0
1

1
1

1
0
1

10

11

12

13

14

15

16

17

18

19

1
0
1

1
0

1
1
0
1

1
1
0
1

1
0
1

1
0
0
1

1
0
1

1
0
1

1
0
1

Table 1 Huckel Matrix for Triphenylmethyl Radical

All calculations were conducted using the Huckel Molecular Orbitals (HMO) Calculations computer
program, Copyright 1993 by David R. Anderson, Department of Chemistry, University of Colorado,
Colorado Springs, CO 80933.