Hückel's rule

Benzene, the most widely recognized aromatic

compound with six (4n + 2, n = 1) delocalized
electrons.

In organic chemistry, Hückel's rule

estimates whether a planar ring molecule
will have aromatic properties. The
quantum mechanical basis for its
formulation was first worked out by
physical chemist Erich Hückel in 1931.[1][2]
The succinct expression as the 4n + 2 rule
has been attributed to W. v. E. Doering
(1951),[3][4] although several authors were
using this form at around the same time.[5]

In keeping with the Möbius-Hückel

concept, a cyclic ring molecule follows
Hückel's rule when the number of its π-
electrons equals 4n + 2 where n is a non-
negative integer, although clearcut
examples are really only established for
values of n = 0 up to about n = 6.[6]
Hückel's rule was originally based on
calculations using the Hückel method,
although it can also be justified by
considering a particle in a ring system, by
the LCAO method[5] and by the Pariser–
Parr–Pople method.

Aromatic compounds are more stable than

theoretically predicted using
hydrogenation data of simple alkenes; the
additional stability is due to the
delocalized cloud of electrons, called
resonance energy. Criteria for simple
aromatics are:

1. the molecule must have 4n + 2

electrons in a conjugated system of p
orbitals (usually on sp2-hybridized atoms,
but sometimes sp-hybridized);
2. the molecule must be (close to) planar
(p orbitals must be roughly parallel and
able to interact, implicit in the requirement
for conjugation);
3. the molecule must be cyclic (as
opposed to linear);
4. the molecule must have a continuous
ring of p atomic orbitals (there cannot be
any sp3 atoms in the ring).

Monocyclic hydrocarbons
The rule can be used to understand the
stability of completely conjugated
monocyclic hydrocarbons (known as
annulenes) as well as their cations and
anions. The best-known example is
benzene (C6H6) with a conjugated system
of six pi-electrons, which equals 4n + 2 for
n = 1. The molecule undergoes
substitution reactions which preserve the
six pi-electron system rather than addition
reactions which would destroy it. The
stability of this pi-electron system is
referred to as aromaticity. Still, in most
cases, catalysts are necessary for
substitution reactions to occur.

The cyclopentadienyl anion (C5H–

5 ) with six
pi electrons is considerably more stable
than either the neutral cyclopentadienyl
radical with five pi electrons or the
corresponding cation with four.[7] Similarly
the tropylium cation (C7H+7) has six pi
electrons and is more stable than either
the cycloheptatrienyl radical (C7H•7) or its
anion.[7] The cyclopropenyl cation (C3H+3)
[8][9] and the triboracyclopropenyl dianion
(B3H2–
3 ) are considered examples of a 2π-
electron system [10][11]

Planar ring molecules with 4n pi electrons

do not obey Hückel's rule, and theory
predicts that they are less stable and have
triplet ground states with two unpaired
electrons. In practice such molecules
distort from planar regular polygons.
Cyclobutadiene (C4H4) with four pi
electrons is stable only at temperatures
below 35 K and is rectangular rather than
square.[7] Cyclooctatetraene (C8H8) with
eight pi electrons has a nonplanar "tub"
structure. However the dianion C8H2–
8
(Cyclooctatetraenide anion), with ten pi
electrons obeys the 4n + 2 rule for n = 2
and is planar.[7]

Refinement
Hückel's rule is not valid for many
compounds containing more than three
fused aromatic nuclei in a cyclic fashion.
For example, pyrene contains 16
conjugated electrons (8 bonds), and
coronene contains 24 conjugated
electrons (12 bonds). Both of these
polycyclic molecules are aromatic, even
though they fail the 4n + 2 rule. Indeed,
Hückel's rule can only be theoretically
justified for monocyclic systems.[5]

Three-dimensional rule
In 2000, Andreas Hirsch and coworkers in
Erlangen, Germany, formulated a rule to
determine when a fullerene would be
aromatic. They found that if there were
2(n + 1)2 π-electrons, then the fullerene
would display aromatic properties. This
follows from the fact that an aromatic
fullerene must have full icosahedral (or
other appropriate) symmetry, so the
molecular orbitals must be entirely filled.
This is possible only if there are exactly
2(n + 1)2 electrons, where n is a
nonnegative integer. In particular, for
example, buckminsterfullerene, with 60 π-
electrons, is non-aromatic, since 60 ÷ 2 =
30, which is not a perfect square.[12]

In 2011, Jordi Poater and Miquel Solà,

expanded the rule to determine when a
fullerene species would be aromatic. They
found that if there were 2n2 + 2n + 1 π-
electrons, then the fullerene would display
aromatic properties. This follows from the
fact that an spherical species having a
same-spin half-filled last energy level with
the whole inner levels being fully filled is
also aromatic.[13]

See also
Möbius–Hückel concept
Baird's rule

References
1.
Hückel, Erich (1931).
"Quantentheoretische Beiträge zum
Benzolproblem I. Die
Elektronenkonfiguration des Benzols
und verwandter Verbindungen". Z.
Phys. 70 (3–4): 204–86.
Bibcode:1931ZPhy...70..204H .
doi:10.1007/BF01339530 .
Hückel, Erich (1931).
"Quanstentheoretische Beiträge zum
Benzolproblem II. Quantentheorie der
induzierten Polaritäten". Z. Phys. 72
(5–6): 310–37.
Bibcode:1931ZPhy...72..310H .
doi:10.1007/BF01341953 .
Hückel, Erich (1932).
"Quantentheoretische Beiträge zum
 Problem der aromatischen und
ungesättigten Verbindungen. III". Z.
Phys. 76 (9–10): 628–48.
Bibcode:1932ZPhy...76..628H .
doi:10.1007/BF01341936 .
2. Hückel, E. (1938). Grundzüge der Theorie
ungesättiger und aromatischer
Verbindungen. Berlin: Verlag Chem. pp. 77–
85.
3. Doering, W. VON E.; Detert, Francis L.
(1951-02-01). "CYCLOHEPTATRIENYLIUM
OXIDE" . Journal of the American Chemical
Society. 73 (2): 876–877.
doi:10.1021/ja01146a537 . ISSN 0002-
7863 .
4. Doering, W. v. E. (September 1951).
"Abstracts of the American Chemical
Society Meeting, New York": 24M.
5. Roberts, John D.; Streitwieser, Andrew, Jr.;
Regan, Clare M. (1952). "Small-Ring
Compounds. X. Molecular Orbital
Calculations of Properties of Some Small-
Ring Hydrocarbons and Free Radicals". J.
Am. Chem. Soc. 74 (18): 4579–82.
doi:10.1021/ja01138a038 .
6. March, Jerry (1985), Advanced Organic
Chemistry: Reactions, Mechanisms, and
Structure (3rd ed.), New York: Wiley, ISBN 0-
471-85472-7
7. Levine, I. N. (1991). Quantum chemistry
(4th ed.). Prentice-Hall. pp. 559–560.
ISBN 0-205-12770-3.
8. March, Jerry (1985), Advanced Organic
Chemistry: Reactions, Mechanisms, and
Structure (3rd ed.), New York: Wiley, ISBN 0-
471-85472-7
9. Breslow, Ronald; Groves, John T. (1970).
"Cyclopropenyl cation. Synthesis and
characterization". J. Am. Chem. Soc. 92 (4):
984–987. doi:10.1021/ja00707a040 .
10. Wrackmeyer, B. (2016). "A
Cyclotriborane Dianion and the Triboron
Cation: "Light Ends" of the Hückel Rule".
Angew. Chem. Int. Ed. 55 (6): 1962–64.
doi:10.1002/anie.201510689 .
11. Kupfer, T.; Braunschweig, H.; Radacki, K.
(2015). "The Triboracyclopropenyl Dianion:
The Lightest Possible Main-Group-Element
Hückel π Aromatic". Angew. Chem. Int. Ed.
54: 15084–15088.
doi:10.1002/anie.201508670 .
12. Hirsch, Andreas; Chen, Zhongfang; Jiao,
Haijun (2000). "Spherical Aromaticity in Ih
Symmetrical Fullerenes: The 2(N+1)2 Rule".
Angew. Chem. Int. Ed. Engl. 39 (21): 3915–
17. doi:10.1002/1521-
3773(20001103)39:21<3915::AID-
ANIE3915>3.0.CO;2-O ..
13. Poater, Jordi; Solà, Miquel (2011).
"Open-shell spherical aromaticity: the 2N2 +
2N + 1 (with S = N + 1⁄2) rule". Chem.
Comm. 47 (42): 11647–11649.
doi:10.1039/C1CC14958J ..

Retrieved from
"https://en.wikipedia.org/w/index.php?
title=Hückel%27s_rule&oldid=841800147"

Last edited 5 months ago by DMacks

Content is available under CC BY-SA 3.0 unless

otherwise noted.