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31 views5 pages

FDKHFJHFJDSH

Uploaded by

E-Hamdan
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HETEROLYTIC BOND CLEAVAGES

Simple bond cleavages can proceed with the shared pair ultimately residing
on either of the previously joined elements. In either case one atom has a
sextet electronic structure and a positive charge. The other has a valence
octet with at least one lone pair (the pair that was formerly shared) and a
negative charge. Such bond cleavage, in which the previously shared pair
goes with one of the bonded atoms, is termed heterolytic cleavage and
necessarily results in the formation of charged species.

In general, the movement of electrons during heterolytic


cleavage follows the direction of bond polarity. In a polar covalent bond the
shared pair is displaced toward the more electronegative element. Upon
cleavage the pair of bonded electrons are transferred completely to the
more electronegative element, which becomes negatively charged, and the
more electropositive element loses the bonded electron pair and becomes
positively charged.
A species having a carbon atom possessing sextext of electrons and a
positive charge is called a carbocation (earlier called carbonium ion). The C
 H3 ion is known as a methyl cation or methyl carbonium ion.
Carbocations are classified as primary, secondary or tertiary depending on
whether one, two or three carbons are directly attached to the positively
charged carbon. Some other examples of carbocations are: CH3C + H2
(ethyl cation, a primary carbocation), (CH3) 2C + H (isopropyl cation, a
secondary carbocation), and (CH3) 3C + (tert-butyl cation, a tertiary
carbocation). Carbocations are highly unstable and reactive species.
Alkyl groups directly attached to the positively charged carbon stabilise the
carbocations due to inductive and hyperconjugation effects. The observed
order of carbocation stability is: C + H3 < CH3C + H2 < (CH3) 2C + H <
(CH3) 3C + .

It is a general principle in chemistry that the more a charge is dispersed,


the more stable is the species carrying the charge. Put simply, a species in
which a positive charge is shared between two atoms would be more stable
than a similar species in which the charge is borne wholly by a single atom.
In a tertiary

carbocation, the positively charged carbon atom attracts the bonding


electrons in the three carbon-carbon sigma (σ) bonds, and thus creates
slight positive charges on the carbon atoms of the three surrounding alkyl
groups (and, indeed, on the hydrogen atoms attached to them). Chemists
sometimes use an arrow to represent this inductive release:

The overall charge on the carbocation remains unchanged, but some of


the charge is now carried by the alkyl groups attached to the central carbon
atom; that is, the charge has been dispersed.

In the tertiary carbocation shown above, the three alkyl groups help to
stabilize the positive charge. In a secondary carbocation, only two alkyl
groups would be available for this purpose, while a primary carbocation has
only one alkyl group available. Thus the observed order of stability for
carbocations is as follows:

tertiary > secondary > primary > methyl.

Carbocations are sp2 hybridized because, With three bond pairs and zero
lone pairs it has trigonal planar geometry by VSEPR theory, and trigonal
planar is characteristic of sp2 hybridisation. ... A carbocation has only 3
electrons and it has to form 3 sigma bonds with its substituents.
The heterolytic cleavage can also give a species in which carbon gets the
shared pair of electrons. For example, when group Z attached to the
carbon leaves without electron pair, the methyl anion is formed. Such a
carbon species carrying a negative charge on carbon atom is called
carbanion. Carbanions are also unstable and reactive species. The organic
reactions which proceed through heterolytic bond cleavage are called ionic
or heteropolar or just polar reactions.

Carbocation

Structure

Carbocations typically have three substituents which makes the carbon


sp2 hybridized and gives the overall molecule a trigonal planar geometry.
The carbocation's substituents are all in the same plane and have a bond angle of
120o between them. The carbon atom in the carbocation is electron deficient; it
only has six valence electrons which are used to form three sigma covalent bonds
with the substituents. The carbocation carbon has an unoccupied p orbital which is
perpendicular to the plane created by the substituents. The p orbital can easily
accept electron pairs during reactions making carbocations excellent Lewis acids.

A positively charged species such as a carbocation is very electron-poor, and thus


anything which donates electron density will help to stabilize it. Conversely,
a carbocation will be destabilized by an electron withdrawing group.
Stability of carbanions decreases as we are moving from primary to tertiary
carbanion. Because of the +I effect, the methyl groups increase the intensity of the
negative charge on central carbon in tertiary carbanion which makes tertiary
carbanion more unstable.
In homolytic cleavage, one of the electrons of the shared pair in a covalent bond
goes with each of the bonded atoms. Thus, in homolytic cleavage, the movement
of a single electron takes place instead of an electron pair. The single electron
movement is shown by ‘half-headed’ (fish hook: ) curved arrow. Such cleavage
results in the formation of neutral species (atom or group) which contains an
unpaired electron. These species are called free radicals. Like carbocations and
carbanions, free radicals are also very reactive. A homolytic cleavage can be
shown as:
Alkyl radicals are classified as primary, secondary, or tertiary. Alkyl radical
stability increases as we proceed from primary to tertiary: Organic reactions, which
proceed by homolytic fission are called free radical or homopolar or nonpolar
reactions. Homolytic bond cleavage most often happens between two atoms of
similar electronegativity.
The stability of free radicals is dependent on their structure. Free radicals are
species that have an odd number of electrons in the outer or valence shell. They are
very reactive and unstable because they tend to either donate or accept an electron.

A reagent that brings an electron pair is called a nucleophile (Nu:) i.e., nucleus
seeking. A reagent that takes away an electron pair is called electrophile (E+) i.e.,
electron seeking ..
Some examples of nucleophiles are the negatively charged ions with lone pair of electrons such as
hydroxide (HO– ), cyanide (NC– ) ions and carbanions (R3C:– ). Neutral
molecules such as etc., can also act as nucleophiles due to the presence of lone pair
of electrons. Examples of electrophiles include carbocations ( CH3  ) and neutral
molecules having functional groups like carbonyl group (>C=O) or alkyl halides
(R3C-X, where X is a halogen atom). The carbon atom in carbocations has sextet
configuration; hence, it is electron deficient and can receive a pair of electrons
from the nucleophiles
Alkyl halides are excellent electrophiles because halogens share a
polar bond with carbon, are polarizable, and form relatively stable
leaving groups as halide anions

The electron displacement in an organic molecule may take place either in the
ground state under the influence of an atom or a substituent group or in the
presence of an appropriate attacking reagent. The electron displacements due to the
influence of an atom or a substituent group present in the molecule cause
permanent polarlisation of the bond. Inductive effect and resonance effects are
examples of this type of electron displacements. Temporary electron displacement
effects are seen in a molecule when a reagent approaches to attack it. This type of
electron displacement is called electromeric effect or polarisability effect

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