Electrophile

An electrophile is an electron pair acceptor. Electrophiles are positively charged or neutral species
having vacant orbitals that are attracted to an electron rich center. It participates in a chemical reaction by
accepting an electron pair in order to bond to a nucleophile. Because electrophiles accept electrons, they
are Lewis acids. Most electrophiles are positively charged, have an atom that carries a partial positive
charge, or have an atom that does not have an octet of electrons. Example: Br+, CH3+, NH4+BF3,AlCl3,
FeCl3etc.

Electrophilic reagents are of two types.

(a) Positive Electrophiles that are deficient in two electrons and carry a positive charge e.g. : Br+, CH 3+,
NH4+etc.
(b) Neutral Electrophiles whose central atom is electron deficient but no charge e.g. BF 3,AlCl3, FeCl3etc.

➢ Sulphur trioxide is an electrophile because it is a highly polar molecule with a fair

amount of positive charge on the sulphur atom. It is this which is attracted to the ring
electrons. The second stage of the reaction involves a transfer of the hydrogen from the
ring to the negative oxygen.

➢ AlCl3 is a neutral compound but still is an electrophile. The reason can be attributed to
the presence of incomplete octet around aluminium. As seen Al has only 6 electrons
 around it which makes it as well as the whole compound electron deficient. Hence it is
an electrophile.

➢ Triplet nitrenes are thermodynamically more stable and therefore is the strongest
electrophile.

Nitrene

➢ Why BF3 / FeCl3 is electrophile?

Nucleophile
A nucleophile is a chemical species that donates an electron pair to form a chemical bond in
relation to a reaction. All molecules or ions with a free pair of electrons or at least one pi bond
can act as nucleophiles. Because nucleophiles donate electrons, they are by definition Lewis
bases. Example:- Cl- , OH- , CN-, NH3 , H2O etc.

Nucleophilic reagents are of two types.

(a) Negative Nucleophiles which have an excess electron pair and carry negative charge e.g.
Cl- , OH- , CN- etc.

(b) Neutral Nucleophiles which possess spare pairs of electrons, but no charge e.g. -, NH3 , H2O
etc.
➢ A nitrogen atom is larger than an oxygen atom. Therefore, the outer electrons are
held more loosely and are more easily donated as a nucleophile.

➢ Ammonia is a nucleophile because it has a lone pair of electrons and a δ⁻ charge on

the N atom. A nucleophile is a reactant that provides a pair of electrons to form a new
covalent bond. And nitrogen is more electronegative than hydrogen, so the nitrogen
atom has a δ⁻ charge.

➢ NH3(Ammonia) has the stronger nucleophilic character than water molecule.

Because, the Oxygen in the water molecule doesn't likely to bond with any carbon atom
compared to Nitrogen atom. Since Oxygen has more electronegativity than Nitrogen.
Hence it holds onto its lone pair tightly than Nitrogen.

➢ SH- anion is more nucleophilic than OH- anion as the negative charge is more stable
on oxygen atom than sulphur, because of higher electronegativity of oxygen.
Carbocation
A carbocation is a molecule in which a carbon atom has a positive charge and three bonds. We can
basically say that they are carbon cations. Formerly, it was known as carbonium ion. Carbocation
today is defined as any even-electron cation that possesses a significant positive charge on the
carbon atom.
Talking about some general characteristics, the carbon cations are very reactive and unstable due to
an incomplete octet. In simple words, carbocations do not have eight electrons, therefore they do not
satisfy the octet rule.

In carbocation, the hybridization of carbon will be sp2 and its shape is trigonal planar. There is also a
vacant p orbital which indicates its electron-deficient nature. The carbon has 6 electrons in its
valence shell. Due to this, it is an electron-deficient species, also known as an electrophile.
A carbocation is generally observed in an SN1 reaction, elimination reaction, etc.

Classification of Carbocation
The different carbocations are named on the basis of the number of carbon groups bonded to the
carbon. The carbocation can be termed as methyl, primary, secondary or tertiary on the basis of how
many carbon atoms are attached to it:

• Methyl carbocation: If no carbon is attached to the carbon with the positive charge it is simply
called as methyl carbocation.
• If one, two or three carbon is attached to the carbon with the positive charge it is called
the primary carbocation, secondary carbocation, tertiary carbocation respectively.
 • If there is a carbon-carbon double bond next to the carbon with the positive charge it is
termed as allylic carbocation.
• In the same way, if the carbon with the positive charge is attached to a double bond, the
carbocation is termed as vinylic carbocation. Here, hybridization of the carbon having the
positive charge is sp and geometry is linear.
• Whenever the carbon which consists of the positive charge is part of a benzene ring, then
the carbocation an aryl carbocation.
• If the carbon having a positive charge is immediately next to a benzene ring, it is termed as
a benzylic carbocation.
Interestingly, in addition to these types, there is another type of carbocation which is known as
pyramidal carbocation. In this type, the ions consist of a single carbon atom that usually tends to
hover over a four- or five-sided polygon which can be depicted as a pyramid. The 4 sided pyramidal
ion will consist of +1 charge while the five-sided pyramid will have +2 charge.

Formation of the Carbocation

The carbocations can be formed by either of the following two fundamental steps:

• Cleavage of bond of carbon.

• Electrophilic addition.

Cleavage of Bond of Carbon

Whenever there is cleavage of the bond of carbon and atoms attached to it, the leaving group takes
away the shared electrons. Thus leaving the carbon atom as electron deficient. As a result, a
positive charge is developed forming a carbocation. The more tendency of cleavage of bond or
formation of a more stable carbocation the lower is the activation energy.
In many organic reactions such as the SN1 and E1 reactions carbocation is formed as a reaction
intermediate.

Electrophilic Addition
In electrophilic addition, an electrophile attacks on unsaturated point(double or triple bond), this
results in the breaking of the pi bond which results in the formation of a carbocation. The more stable
is the carbocations the lower is the activation energy and faster addition. Electrophilic addition to a pi
bond is illustrated by the reaction of HBr (an electrophile) with propene (CH3CH = CH2).
It can be noted that the formation of the secondary carbocation is favoured over the primary
carbocation because secondary carbocation is more stabilized due to resonance. This is also in
accordance with Markovnikov’s Rule. Such electrophilic addition reactions are generally seen in
alkenes, alkynes and benzene rings.
As we know that the carbocations are very reactive due to their electron deficiency, vacant orbital
and incomplete octet. Therefore, its stability depends on the octet completion and reducing the
electron deficiency.
The stability of a carbocation can be achieved by the following processes:
(a) Addition of a nucleophile.
(b) Formation of a pi bond.
(c) Rearrangement.

Addition of a Nucleophile
A carbocation is electron-deficient and with an incomplete octet and a positive charge on it. The
positive charge is stabilized by the addition of a nucleophile thus the formation of a new covalent
bond takes place. This stabilizes the carbocation. This is a very common process of stabilization of
carbocation because the carbocation is very reactive so even weak nucleophile gets attached to the
carbocation.

Formation of a Pi Bond
The carbocation can receive electrons form nearby hydrogen to remove its positive charge and to
complete its octet. Thus a new pi bond can be formed. The hydrogen atom is generally must be
removed by any base. Due to the high reactivity of the carbocations even a weak base such as
water or iodide ion are able to facilitate the deprotonation. Whenever such deprotonation occurs two
types of products are formed. The more stable compound is the major product.

Rearrangement
The bonding electrons of a carbocation can be shifted between adjacent atoms so that more stable
carbocation can be formed. For instance, rearrangement will be highly favoured if there is a
conversion of a secondary carbocation can be formed from a primary carbocation The reason is
simple because the carbocation is more stabilized in secondary carbocation than in a primary
carbocation.
The different types of carbocation rearrangement are:
Hydride Shifting
Here hydrogen is shifted from 1st carbon to 2nd carbon. So the carbocation has changed from
primary to the secondary carbocation. Thus forming a more stable structure.
Methyl shifting
Here methyl group shifts to the primary carbon to form a more stable structure. The carbocation is
secondary carbocation, so more stable than primary carbocation.

Phenyl shifting
The entire phenyl group can also be shifted to obtain a more stable secondary or tertiary carbocation
than a primary carbocation. This is also interesting to know that phenyl shift is more favoured than a
methyl shift.

Carbocation Stability
The stability order of carbocation is as follows:

The stability of carbocations depends on the following factors:

1. Resonance: Stability of carbocations increases with the increasing number of resonance. More
the number of resonating structures more is the stability of the carbocation. The reason for this is the
delocalization of the positive charge. The electron deficiency is decreased due to the delocalization
and thus it increases the stability.
When compared to substitution, the resonance effect proves to be a more dominating factor than
substitution. Therefore, structures with resonance are far better stabilised than others. Cyclopropane
carbocation is exceptionally very stable due to dancing resonance. Thus tricyclo propane
carbocation is the most stable carbocation.
2. Hyperconjugation and inductive effect: Increasing substitution, increases the hyperconjugation
and thus it increases stability. More the hyperconjugation more is the stability.
R3C+ (3o ; most stable) > R2CH+ (2o ) > RCH2+ (1o) CH3+ (methyl; least stable)
The Carbocation stability depends on the number of carbon groups attached to the carbon carrying
the positive charge.

3. Electronegativity: Electronegativity indicates the capacity of an atom to attract electrons. The

more is the electronegativity, the more is the attraction of the electrons towards the atom. Therefore
the electronegativity of the carbon with the positive directly affects the stability of the carbocation. So
as the electronegativity of the carbon atom increases the stability of the carbocation decreases. sp >
sp2 > sp3 ( sp has maximum s character; so maximum electronegativity, sp3 has minimum s
character; so minimum electronegativity).
The hybridisation of the carbon with the positive charge in the vinylic carbocation is sp whose
electronegativity is more than the sp2 hybridized carbon of the alkyl carbocation. Due to this reason,
the stability of a primary vinylic carbocation is less than a primary alkyl carbocation.
In the same way, lower stability of aryl carbocation in comparison to a secondary alkyl carbocation
can be explained. Vinyl and aryl carbocations are very rare to find due to their low stability.
Carbanion
A carbanion is an anion in which carbon is trivalent (forms three bonds) and bears a formal
negative charge (in at least one significant resonance form).This is a convenient approximation,
although these species are almost always multinuclear clusters containing polar covalent bonds
rather than true carbanions.

Stability of carbanion:

Stability order of carbanions decreases as we move from primary to tertiary anion because due
to +I effect of methyl groups there is an increased intensity of negative charge on central carbon
of tertiary carbanion which further makes it unstable.

1. Understanding The Stability Of Negative

Charge Helps Us Understand What Reactions
Are Likely (And Not Likely) To Occur
Let’s talk about a concrete example. For instance if a reaction leads to the formation of a very
unstable negative charge, it’s unlikely to occur. But if it leads to the loss of a very unstable
negative charge, it’s considerably more likely.

For instance, that’s why one of these reactions of methane is likely and the other is unlikely.
These acid-base reactions are covered here, BTW.

So what factors lead to the stabilization of negative charge? Two main things.

1. negative charge is stabilized by adjacent positive charge (opposite charges attract!)

2. negative charge tends to be less stable when it’s concentrated and more stable when
it’s dispersed.

Think about that as you look at this list of seven factors that stabilize negative charge.

2. Factor #1: High Charge Densities Are

Unstable
This one’s fairly straightforward to understand. High charge densities are unstable. So as we
move from water to HO(–) to O(2-), we are getting progressively more unstable here. This is
reflected in acidity tables; water (H2O) is far more likely to lose a proton to give HO(–) than
HO(–) is likely to lose a proton to give O(2-)
3. Factor #2: As Electronegativity Increases
Across The Periodic Table, So Does The
Stability Of Negative Charge
Electronegativity is a rough measure how effectively the positively charged nucleus of an atom
can “pull” electrons toward it. (Opposite charges attract.) Electronegativity increases as we go
across the periodic table. So if you compare the anions going from C , N, O to F across the
periodic table, the stability of the negative charge will increase. This is also reflected in acidity
values.

4. Factor #3: As Polarizability Increases Down

The Periodic Table, So Does The Stability Of
Negative Charge
Down the periodic table, it’s a little more helpful to think “dispersal of charge is good!” rather
than “opposite charges attract”. Compare fluorine and iodine. The size of the fluorine ion
(radius: 119 pm) is much smaller than iodine (radius: 206 pm). However, they both have a
charge of negative 1.

Imagine two balls, each weighing one pound. But one is made of iron, and the other is made of
rubber. Which ball is going to be smaller? The iron ball (smaller and harder – more dense) is like
fluorine, and the rubber ball (larger and squishier) is like iodine. And a certain “squishiness”
helps to stabilize charge, since it isn’t as concentrated over a small volume. That’s a way of
expressing the greater polarizability of iodine. Low charge densities are more stable!

5. Factor #4: Resonance Stabilization Of

Negative Charge
Along the same lines, a negative charge that is adjacent to one or more Pi bonds can disperse its
negative charge over multiple atoms. We describe this phenomenon as “resonance”. So in the
example below, the negatively charged alkane on the left is much less stable than the adjacent
negatively charged species, where the negative charge can be dispersed over multiple carbons
through resonance. This is another example of how reducing charge density (or spreading it out)
is a stabilizing influence.
6. Factor #5: Electron-Withdrawing Groups
(Inductive Effects) Stabilize Negative Charge
This one falls more into the auspices of “opposite charges attract”. A negative charge that is
adjacent to an atom with electron withdrawing groups on it will be much more stable than an
equivalent atom that is not. In the extreme case of CCl3(-), the resulting ion is many orders of
magnitude more stable than H3C(-) itself. (This is the basis of the haloform reaction).

7. Increasing s-Character In The Hybridization

Of An Atom Is Effectively Like Increasing Its
Electronegativity
s orbitals are closer to the nucleus than p orbitals are. So electrons that are in s orbitals will be
closer to the nucleus than electrons in p orbitals – and therefore, lower in energy (“opposite
charges attract”). For this reason, electrons that are in sp orbitals are lower energy than sp2,
which is lower energy than sp3, since they have greater s character (33% for sp2) than sp3 (25%).
This makes the anions more stable, just as if it were on a more electronegative atom.

8. A Special Case: Aromaticity

This is a special case, covered in detail in organic chemistry 2 (peek ahead). Certain molecules
possess a special stability – called aromaticity – that is enormously stabilizing, kind of like
qualifying for a huge tax break from the government. Certain negatively charged molecules –
such as the cyclopentadienyl anion, pictured below – are aromatic, and therefore possess much
greater stability than they would have otherwise.

9. “Basicity” Is Just Another Word For

“Stability Of The Negative Charge”
 Seven factors?!!! So how do we know which is most important? That’s a great question! These
trends can interact with each other in unpredictable ways, and it’s hard to judge which is most
important.

Thankfully, there’s a concept you’ve probably already met for figuring out the stability of these
species, which can be readily measured. It’s called basicity. These factors determine how stable
a base will be!

The basicity of a species tells you about how stable its lone pair of electrons are.

How do we find a good measure of basicity? Simple. It’s in the pKa table, a collection of
measurements that’s been compared to the table of hand strengths in poker.

Bottom line:

• Two factors to watch out for: opposite charges attract, and dispersal of charge.

• unstable anions will tend to be at the intial tails of arrows (form bonds).

• stable anions will tend to be at the final heads of arrows (likely to be leaving groups)

Next Post: Curved Arrows in Organic Chemistry (2) Initial Tails and Final Heads
00 General Chemistry Review
01 Bonding, Structure, and Resonance
02 Acid Base Reactions
03 Alkanes and Nomenclature
04 Conformations and Cycloalkanes
05A Primer On Organic Reactions
• The Most Important Question To Ask When Learning a New Reaction
• The 4 Major Classes of Reactions in Org 1
• Learning New Reactions: How Do The Electrons Move?
• How (and why) electrons flow
• The Third Most Important Question to Ask When Learning A New Reaction
• 7 Factors that stabilize negative charge in organic chemistry
• 7 Factors That Stabilize Positive Charge in Organic Chemistry
• Common Mistakes: Formal Charges Can Mislead
• Nucleophiles and Electrophiles
• Curved Arrows (for reactions)
• Curved Arrows (2): Initial Tails and Final Heads
• Nucleophilicity vs. Basicity
• The Three Classes of Nucleophiles
• What Makes A Good Nucleophile?
• Leaving Groups Are Nucleophiles Acting In Reverse
• What makes a good leaving group?
• 3 Factors That Stabilize Carbocations
• Three Factors that Destabilize Carbocations
• What's a Transition State?
• Hammond's Postulate
• Grossman's Rule
• Draw The Ugly Version First
• Learning Organic Chemistry Reactions: A Checklist (PDF)
• Introduction to Addition Reactions
• Introduction to Elimination Reactions
• Introduction to Free Radical Substitution Reactions
• Introduction to Oxidative Cleavage Reactions
06 Free Radical Reactions
07 Stereochemistry and Chirality
08 Substitution Reactions
09 Elimination Reactions
10 Rearrangements
11 SN1/SN2/E1/E2 Decision
12 Alkene Reactions
13 Alkyne Reactions
14 Alcohols, Epoxides and Ethers
15 Organometallics
16 Spectroscopy
17 Dienes and MO Theory
18 Aromaticity
19 Reactions of Aromatic Molecules
20 Aldehydes and Ketones
21 Carboxylic Acid Derivatives
22 Enols and Enolates
23 Amines
24 Carbohydrates
25 Fun and Miscellaneous