Carbanions and Free Radicals

ADVANCED ORGANIC CHEMISTRY I (MPC 102T) UNIT- I: Basic Aspects of Organic Chemistry
CARBANIONS
- A carbanion is an anion in which carbon is tetravalent (forms three bonds) and bears a formal negative charge in
at least one significant mesomeric contributor (resonance form).
- Absent delocali ation, carbanions assume a trigonal pyramidal, bent, or linear geometry when the carbanionic
carbon is bound to three (e.g., methyl anion), two (e.g., phenyl anion), or one (e.g., acetylide anion) substituents,
respectively.
- Formally, a carbanion is the conjugate base of a carbon acid: R3C-H + B R3C + HB

(where B stands for the base)
-
Characteristic of Carbanions:
(i) Hybridisation and geometry: Alkyl carbanion has three bond pairs and one lone pair. Thus
hybridisation is sp3 and geometry is pryamidal. [Note: Geometry of allyl and benzyl cabanion is
almost planar and hybridisation is sp2].
(ii) There are eight electrons in the outermost orbit of carbanionic carbon hence its octet is complete.
(iii) It behaves as charged nucleophile.
(iv) It is diamagnetic in character because all eight electrons are paired.
(v) It is formed by heterolytic bond fission.
(vi) It reacts with electrophiles.
Structure of Carbanion:
- As carbanion have one non-bonding and three bonding electron pair in four sp3 hybridised orbital.
- The non-bonding electron pair repels the bonding pair more than the bonding pairs repel each other and because
of this, there is reduction of the angle between bonding pairs to a value slightly lesser than the tetrahedral value of
109.5°.
- The configuration of simple carbanions such as the methyl anion thus appears to be pyramidal just like that of
ammonia with which the methyl anion is isoelectronic.
- If the three substituents of carbanion are different, then the carbanion should be asymmetric and consequently
there should be retention of configuration in the reactions involving a carbanion intermediate. However, it could
not be demonstrated experimentally as the unshared pair and the central carbon rapidly oscillate from one side of
the plane to the other. This rapid equilibrium between enantiomeric pyramidal structures thus explains the loss of
optical activity associated with the asymmetric carbanions.
Lecturer Notes_Dr. Sumanta Mondal_M. Pharm (Pharmaceutical Chemistry) _GITAM University Page | 10
E-mail: logonchemistry@gmail.com; phytochemistry@rediffmail.com
Formation of carbanions:
(a) When a group or atom departs from a carbon atom without its bonding pairs
(b) When a negative ion attacks on alkynes or alkenes
(c) Abstraction of proton by a strong base from carbonyl compounds or nitro compounds.
Effect of electron withdrawing group on formation of carbanions:

- As there is little difference between the electro negativities of carbon and hydrogen, the polarity of the C H
bond is very small.
- The heterolytic fission of this covalent bond to form an anion and a proton should then be a very difficult process.
In other words, a hydrogen atom bound to a carbon atom shows negligible acidity.
- However, the presence of electron attracting substituents such as nitro, cyano or carbonyl groups on the same
carbon renders the hydrogen relatively acidic.
- The increase in acidity is not only due to the electron-withdrawing ability of these substituents, but also due to
their ability to delocalize the negative charge of the anion. Thus hydrogens on the carbon atom alpha to nitro,
cyano or carbonyl groups have acidic character and can be removed as protons leaving resonance stabilized
anions.
Stability of carbanions:
- The entire factors which decrease the negative charge density on carbanion increase its stability. The stability of
carbanion may be affected by following factor:
(A). Electronegativity of carbanionic carbon:
Stability directly proportional to electronegativity of carbanionic carbon which is directly proptional to %
s-character of carbanionic carbon.
sp3 sp2 sp
(i) % s-character in increasing order

(ii) Stability in increasing order.
The negative charge on a carbanion is stabilized by neighboring Electron Withdrawing Groups (EWG)
such as carbonyl, nitro, and sulfone. [EWG = C=O , NO2 , CN , SO2]
The stabilizing dispersal of the electrons into the EWG is shown in the examples below. Carbonyl
functions are very effective in stabilizing adjacent negative charge and when two carbonyl groups are
present (as in diethyl malonate or acetylacetone) a very useful carbanionic intermediate is produced. The
intermediate is called an enolate. The dithane system is capable of stablizing the carbanion by dispersal of
the charge into the d orbitals of the sulfur atoms.
(B). Inductive effect:

Stability of alkyl carbanions can be explained by inductive effect.
1. With increase in +I effect stability decreases
2. With increase in I effect stability increases
Greater the number of alkyl group [+ I effect] attached to the carbon atom bearing negative charge, lesser
is the stability. Because there inductive effect increase negative charge density on the carbon.
(C). Effect of resonance:

A carbanion is stabilized by resonance if a double bond is located to the anionic carbon. Due to
delocalization negative charge diffuse over whole molecule and thus stability increases.
This explains the stability of the allylic and benzylic carbanions.
(D). Stabilisation by Sulphur and Phosphorous:

Attachment of carbanionic carbon of a sulphur and phosphorus atom causes an increase in carbanion
stability. The cause of stability is due to the delocalisation of negative charge of carbanion by vacant
d-orbital of phosphorus and sulphur.
(E). Stabilisation by >C=O, NO2 and CN groups present on carbanionic carbon: These groups stabilise
carbanion by resonance effect.
(F). Stability of Aromatic Carbanions:

Anion in which negative charge is present on carbon of aromatic system is known as aromatic carbanions.
Aromatic carbanions are most stable carbaions because unshared electron pair of carbanion itself take part
in delocalisation.
Anions obeying Huckel rule are stable because they are aromatic and there is complete delocalisation of
negative charge.
Stability of different type of carbanions in decreasing order

Aromatic carbanion > Benzyl carbanion > Allyl carbanion > CH= > CH2= > Alkyl carbanion
Reactions in which product formation takes place by formation of carbanion as reaction intermediate:
In the following reactions product formation takes place by the formation of carbanion as reaction intermediates:-
(i) Condensation reactions of carbonyl compounds, i.e., aldol condensation, Perkin reaction,
reformatsky reaction, manich reaction, Michael reaction.
(ii) Condensation reactions of ester; Claisen condensation.
(iii) Wittig reaction.
FREE RADICALS
Free radicals are chemical species that contain a singly occupied orbital. They are neutral and tend to be highly
reactive.
Free radical reactions do not involve the donation or acceptance of an electron lone pair and they are not ionic.
Instead, free radical reactions operate through homolytic cleavage-that is, bonds break such that equal numbers of
electrons are distributed to each atom.
Formation of Free Radicals: Three general methods are used for the generation of free radicals.
1. Thermal Generation: Two types of compounds dissociate to give free-radicals at moderate temperature:
(i) Compounds that have an intrinsically weak bond such as Dialkyl Peroixides (DO-O = 155 KJ mol-1)
(ii) Compounds that, on fragmentation, form strongly bonded products, such as Azobisisobutyronitrile (AIBN)
which releases N2.
2. Photochemical Generation: Light can bring the fragmentation of a compound if the wavelength of the
light is correspond both to an energy greater than that of the bond to be cleaved, and to an electronic
excitation of the molecule concerned. This procedure is suitable for the formation of alkoxy radicals from
alkyl nitrite or hypochlorites.
3. Redox Generation: Covalent bonds may be broken by electron transfer process either by accepting an
electron from a donor or donating an electron to an acceptor.
Structure of Free Radicals:

The shape and geometry of a free radical based on the theory of hybridization and there can be two basic
shapes of free radical.
If the centre carbon atom of the radical is sp3 hybridized (e.g. CH4), then the geometry will be tetrahedral.
But in the case of a radical there are only three groups attached to the sp3 hybridized carbon atom so they
we will have a shape of what resembles a pyramid-it s a tetrahedron ith its head c t off. .
So sp3 hybridized radicals are pyramidal in shape shallow pyramidal geometry. It is so because, due to the
presence of single electron in the 2pz orbital, it is not completely pyramidal, however, the electron-electron
repulsion forces the bonds to bend from trigonal planar geometry.
Methane
Carbocation: sp2 hybridization, trigonal planar

Carbanion: sp3 hybridization, pyramidal
Free radical: sp3 hybridization, shallow pyramidal geometry. It is so because, due to the presence of
single electron in the 2pz orbital, it is not completely pyramidal, however, the electron-electron repulsion
forces the bonds to bend from trigonal planar geometry.
Now if the C-atom is sp2 hybridized, so the shape would be planar with the single electron in the
unhybridized p-orbital with the three substituents having sp2 hybridized bonds.
Factors That Stabilize Free Radicals

- Stability increases in the order methyl < primary < secondary < tertiary
- Free radicals are stabilized by resonance
- Free radicals are stabilized by adjacent atoms with lone pairs
- Free radicals increase in stability as the electronegativity of the atom decreases
- Free radicals increases in stability as we go down the periodic table (larger size)
- Free radicals decrease in stability as we go from sp3 to sp2 to sp hybridization
- Adjacent electron withdrawing groups decrease the stability of free radicals.
1. Inductive Effect:
Free radicals are electron-deficient species has lacks of octet; it is stabilized by Electron Donating Groups.
Thus, greater the number of alkyl groups attached, more is the stability
Radicals are also stabilized by adjacent atoms with lone pairs, such as oxygen and nitrogen.
- Oxygen does have two lone pairs of electrons. The adjacent oxygen atom can donate electron density
to the half-empty p orbital, which is a stabilizing interaction.
2. Hyperconjugation:
More the number of - hydrogens more will be the stability of the free radical via hyperconjugation.
3. Resonance Effect:
Charge delocalization also stabilizes electron deficient species. Geometry of free radicals is shallow
pyramidal such that the partially filled p-orbital can overlap with adjacent p-orbitals of the π-bonds
resulting in delocalization.
Note the difference in bond strengths between the (primary) C-H bond of propane and of the alkyl C-H
bond of propene. The sizeable difference [~13 kcal/mol] is a reflection of the greater stability of the
resonance-stabili ed all l radical. Altho gh not directl comparable, look at the C-H bond strength when
it is adjacent to two alkenes [76 kcal/mol]. This do bl all lic C H bond is even weaker, reflecting the
fact that a greater number of resonance forms are available for the radical species.
4. Free radicals are stabilized by adjacent atoms with lone pairs:

The difference in bond strengths between the C-H bond of methane [104 kcal/mol] and C-OH methanol
[95 kcal/mol]. In between C-F bond of fluoromethane [101 kcal/mol]. Fluorine is more electronegative
than H, the presence of the lone pairs on F is actually stabilizing relative to H.
5. Across the periodic table, free radical stability decreases with increasing electronegativity:
The most electronegative element has the least stable free radical and this is reflected in the higher bond
strength.
6. Down the periodic table, free radical stability increases with increasing size of the atom:
Bond-dissociation energy (BDE) decreases as we go from H-F [136 kcal/mol] to H-Cl [103 kcal/mol] to
H-Br [87 kcal/mol] to H-I [71 kcal/mol].
The iodide radical is the most stable, since the orbital is larger in si e and is therefore spread o t o er a
larger ol me. F rther a a from the n cle s, therefore feeling less effecti e n clear charge than o ld a
smaller atom.
Free radicals increase in stability going down a column of the periodic table, [F < Cl < Br < I ] since the
electron-deficient orbital is spread out over a greater volume.
Across a row of the periodic table, free radicals decrease in stability as the electronegativity increases.
7. The stability of the free radical depends on Hybridization:

Free radicals decrease in stability as the % of s-character in the orbital increases [i.e. as the half-empty orbital
becomes closer to the nucleus]. For that reason, free radical stability decreases as the atom goes from
sp3 ⟷ sp2 ⟷ sp.
(Note By: The stability of the free radical decreases as the orbital is held closer to the nucleus)
Reactions of Free Radicals
The Characteristics of Free radical Reactions

Free radical reactions may be broadly classified into two groups.
- In the first, the product formation occurs from the combination of two radicals.
- In the second class, the product formation results from the reaction of a radical with a molecule by
chain process

Carbanions and Free Radicals

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Carbanions and Free Radicals

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ADVANCED ORGANIC CHEMISTRY I (MPC 102T) UNIT- I: Basic Aspects of Organic Chemistry

- Formally, a carbanion is the conjugate base of a carbon acid: R3C-H + B R3C + HB

(b) When a negative ion attacks on alkynes or alkenes

Effect of electron withdrawing group on formation of carbanions:

(i) % s-character in increasing order

(B). Inductive effect:

(C). Effect of resonance:

(D). Stabilisation by Sulphur and Phosphorous:

(F). Stability of Aromatic Carbanions:

Stability of different type of carbanions in decreasing order

Structure of Free Radicals:

Carbocation: sp2 hybridization, trigonal planar

Factors That Stabilize Free Radicals

4. Free radicals are stabilized by adjacent atoms with lone pairs:

7. The stability of the free radical depends on Hybridization:

Reactions of Free Radicals

The Characteristics of Free radical Reactions

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