AROMATICITY

OF IONS
WELCOME TO TODAY'S CLASS AGENDA
• Introduction to Aromaticity
• Aromatic ions - overview
• key examples of aromatic ions
• Problems on aromaticity of ions
• Properties of Aromatic ions
• Application and significane of Aromatic ions
• Recent advances and research
 Introduction to Aromaticity
Aromaticity is a concept in chemistry that describes a
particular type of stability found in certain cyclic
(ring-shaped) molecules. The most common examples
are benzene and its derivatives.Understanding
aromaticity helps in predicting the behavior of organic
compounds in chemical reactions and is fundamental
in many areas of chemistry
Aromatic ions - overview
Aromatic Ions are essentially charged
species of aromatic compounds. They could
either be cations, which have been formed
by loss of electrons, or anions, which have
gained electrons.

characteristics of aromatic ions

• They have a cyclomatic planar structure.
• The p-orbitals overlap, forming a conjugated
system of parallel, overlapping electron cloud.
• These ions follow the Hückel rule of (4n + 2) pi
electrons.
• Compounds are usually more stable compared to
corresponding non-aromatic and anti-aromatic
compounds.
 Huckels Rule

1.It must be cyclic

2.It must be planar in nature
3.It should have delocalized pi electron
system
4.This should satisfy Huckel's Rule
 CYCLOPROPENYL CATION
• Ring Structure: The cyclopropenyl cation consists of
a three-membered ring with two carbon-carbon
double bonds.
• Planar Geometry: The ring is planar, which is
essential for effective overlap of π-orbitals and
delocalization of electronπ-Electron Delocalization:
In the cyclopropenyl cation, the π-electrons are
delocalized over the entire ring.
• Huckel’s Rule:For the cyclopropenyl cation:( n = 0 )
fits the rule, as ( 4n + 2 = 2 ) π-electrons.
• Cyclopentadienyl Anion
• Structure: The cyclopentadienyl
anion is a planar, cyclic structure
with five carbon atoms. Each
carbon atom has a p-orbital, and
the anion has six π-electrons (due
to the extra electron from the
negative charge).According to
Hückel's rule, a molecule is
aromatic if it has ((4n + 2)) π-
electrons, where (n) is a non-
negative integer. In the case of
the cyclopentadienyl anion, (n =
1) and it has (4n + 2 = 6) π-
electrons, which fits the rule for
aromaticity.
Pyrylium cation as a type of
aromatic ion
The Pyrylium Ion is an aromatic ion
recognised by its cyclic and planar molecular
structure. It showcases a six-membered ring
with delocalized π-electrons. The molecular
formula for this ion is C5H5O+. In chemistry,
it serves as an essential model for
understanding some facets of aromaticity.
AZULENE
1.Cyclic
2.Planar
3.sp2 hybrid in ring
4.Conjugation
5.Huckel's Rule
 Properties of Aromatic ions

One of the reasons why aromatic ions are fascinating to

study involves their unique properties. These properties
set them apart from other organic ions and contribute to
their extensive usage in chemistry and industry. The
properties of aromatic ions can broadly be classified as
chemical and physical aspects.
Chemical properties of Aromatic ions
• Reactivity: The characteristic stability means
aromatic ions are less reactive than typical ions.
They follow certain select types of reactions that
preserve aromaticity, like electrophilic aromatic
substitution and nucleophilic aromatic substitution
• Preference for Substitution over Addition: In
reactions, aromatic ions prefer substitution over
addition. Addition reactions disrupt the structure's
cyclic electron conjugation, while substitution
reactions preserve the aromatic ring.
• Resonance Energy: Aromatic compounds have
significant resonance stabilisation.The difference
between the energy of the real molecule and the
energy of the most stable contributing structure is
known as the resonance energy, which is
particularly high in aromatic ions.
• Aromatic Transitions: Aromatic ions can readily
Physical Properties of Aromatic ions

• NMR and Magnetic Properties: Aromatic ions show

a distinctive response in NMR spectra due to their
cyclic electron cloud, which induces an unusual
screening environment.
• UV Spectroscopy: The extent of conjugation
affects the absorption of ultraviolet or visible
light. An increase in the degree of conjugation, or
number of double bonds, shifts the absorption
peak to longer wavelengths. Thus, an aromatic
ion's UV-VIS spectrum can indicate its level of
conjugation and give clues about its structure.
• IR Spectroscopy: Infrared spectroscopy (IR) is
another physical property significant for aromatic
ions. The existence of out-of-plane bending
modes in IR spectra can be an indicator of an
aromatic compound.
• Apart from being a prime
example of aromatic ions, APPLICATIONS
Pyrylium ions play a significant AND SIGNIFICANE
role in synthetic chemistry.
Their high reactivity and
OF AROMATIC
stability make them excellent IONS- PYRYLIUM
intermediate compounds in ION
many organic reactions.
• Their reactivity and use in
synthesis have made them
prime targets in pyrylium dye
manufacturing, leading to
numerous new types of
synthetic dyes.
• They also find application as
chemical sensors and
ROLE OF CYCLOPROPENIUM ION IN AROMATICITY REACTIONS

• The cyclopropenium ion, though small in structure, plays a pivotal role in

many organic reactions. This ion's kinetic stability, despite the inherent
“strain” of the three-membered ring, owes to the delocalisation of the π
electrons over the entire molecular framework.
• One of its significant contributions is as a catalyst in certain types of
polymerisation reactions. The ion's stable and conjugated structure makes
it an effective catalyst in initiating reactions, such as ring-opening
polymerisation, where they have an important role in extending the
polymer chain. Furthermore, as an ion, it serves to increase the solubility
of many compounds in water, aiding in various synthesized reactions
typically observed in pharmaceuticals.
• Thus, understanding these aromatic ions and their properties can provide
a solid foundation for your further journey in the intriguing world of
chemistry.
 Recent advances and research
• Extended Aromatic Systems: Researchers have
explored aromaticity in systems with more
complex or extended structures, such as
polycyclic aromatic hydrocarbons and
heterocyclic compounds. These studies reveal
how extended conjugation affects the stability of
aromatic ionsComputational Methods:
• Advances in computational chemistry have
provided more accurate models to predict and
analyze aromaticity in ions. Techniques like
density functional theory (DFT) have become
instrumental in exploring and confirming the
aromatic character of ionic species.
• Experimental Techniques: Improvements in
experimental techniques, such as mass
spectrometry and NMR spectroscopy, have
enabled the direct observation of aromatic ions
and provided empirical evidence supporting
theoretical predictions.
Thank you❤️