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HBR H /PT No Reaction: R C CR
HBR H /PT No Reaction: R C CR
HBr no reaction
H2/Pt
very slowly formed
R2C CR2
no reaction
Diels-Alder
Aromaticity
Aromaticity provides the benefits of high stability, etc. But what is
required for a molecule to be aromatic? There are some simple rules:
1) The molecule must be cyclic
2) This cycle must be fully conjugated
3) The cycle must be planar – maximizes orbital overlap
4) The electrons must be able to “circulate”- hence must be delocalized
1
5) The conjugated cycle must contain 4n+2 π electrons (Huckel’s rule),
where n = 0,1,2,3,4,.....
If the conjugated cycle has only 4n π electrons, it is anti-aromatic, and will
either be highly reactive, or will distort in order to violate one of the other
rules (1-4).
Let’s look at the MO diagram for benzene: we start with six 2p orbitals
hence we get three bonding and three antibonding MO’s – Figure 17.9.
In drawing M.O. diagrams for benzene, the first, most obvious factor is
that while it is possible to draw a diagram where there are no nodes, it is
not possible to draw a diagram where there is only ONE node! This
restriction against having an odd number of nodes (1, 3, or 5) is due to
the cyclic nature of benzene, and the high degree of symmetry involved.
Note that there are two possibilities for MO’s with 2 or 4 nodes. These
MO energy levels have the same energy hence are called degenerate.
Finally, only one MO energy level that has 6 nodes can be drawn.
Thus, there are six MO energy levels, of which two pairs are degenerate;
since there are six 2p electrons, they occupy the 3 lowest energy,
bonding MO’s.
Note that the HOMO is comprised of two degenerate orbitals, as is the
LUMO.
The inscribed polygon (also called a Frost Circle) method can be used to
find the MO energy level diagram for planar, cyclic, fully conjugated
molecules like benzene: the appropriate polygon (same size as the ring) is
inscribed, vertex down, in a circle of radius 2β with the nonbonding line
dividing the circle exactly in half; intersections of the ring with the circle
will mark the positions of the molecular orbitals – see Page 628
We find that:
(1) For conjugated cycles with an EVEN number of atoms, there will be a
single high energy level, and a single low energy level.
2
For conjugated cycles with an ODD number of atoms, there will be a single
low energy level, and a degenerate (i.e. double) high energy level – see
page 629
(2) There are as many MO energy levels as there are atoms, and the rest
come as degenerate pairs!
(3) The “nonbonding” energy level runs through the middle of the
diagram.
3
When a cyclobutadiene derivative that was too sterically hindered to
react was made, it was discovered that the cycle had distorted from the
square arrangement to a rectangular one– in this instance, by strongly
localizing the bonds, and violating rule 4.
What does this distortion do to help out with the half-filled shell? If we
look at the orbital energy levels, we see that the distortion removes some
of the orbital degeneracy (by lowering the molecule’s symmetry). Both
electrons populate the lower energy level:
Notice that this leaves a HOMO and LUMO that are VERY close in energy –
highly conjugated antiaromatic cycles which distort in this way are often
highly colored, because of the closeness of these two energy levels (See
discussion of UV-Vis spectroscopy, Chpt 16).
ii) Cyclooctatetraene:
This molecule contains 8 (4n where n=2) electrons, and is antiaromatic.
Let’s consider the MO diagram for cyclooctatetraene (COT) – draw frost
circe (remember, even number of carbons):
1) a single lowest energy level, a single highest energy level.
2) That leaves 6 more orbitals - arranged as degenerate pairs.
3) Filling in the 8 electrons from the bottom up leaves the nonbonding HOMO
half-filled.
In order to avoid this high energy situation and minimize both angle strain
and torsional strain, it distorts by bending (or folding) into a tub-shape:
4
We’re now violating rule #3 (and 4), and thus avoiding the aromaticity
question altogether.
Is there a way to make anti-aromatic molecules aromatic? Of course -
simply by adding or removing electrons! For example, if cyclooctatetraene
is reduced (electrochemically, or with a metal like K), it easily picks up
two electrons. The resulting dianion is planar, and aromatic (10 π-
electrons). Similarly, cyclopentadiene (non-aromatic) is very easily
deprotonated to form cyclopentadienyl anion (6 π-electrons).
Annulenes:
Aromatic systems that are not comprised of benzene rings (often called
non-benzenoid aromatics) are a fascinating area of chemistry. These
large-ring compounds are called annulenes. One of the most significant
members of this family is [18]annulene (the number in brackets denotes
the number of carbons in the ring and, usually, the number of π
electrons):