NOTE

C H E M I S T R Y

CHEMICAL BONDING
THE MOLECULAR ORBITAL THEORY

What you already know

• Hybridization in odd electron species • NBEPR: Non-bonded electron pair repulsion

• Back bonding

What you will learn

• Back bonding continued • Drago’s compound

Recap

Coordinate bond

There are two types of coordinate bonds.

• Dative bond: 𝛔-type
An atom in a molecule acts as a donor in donating a pair of electrons (N) and an atom in
another molecule acts as an acceptor in accepting a pair of electrons (B). This results in the
formation of an adduct.
Example: H3N: → BF3 (Here, nitrogen acts as a donor and boron acts as an acceptor.)
• 𝛑 back bond: 𝛑-type F
It is a covalent bond resulting from the formation of a molecular
orbital by side-to-side (lateral) overlap of atomic orbitals along a
plane perpendicular to the line connecting the nuclei of the atoms. B
Example: BF3 F F
Back bonding

• It is the transfer of a lone pair of electrons from a filled orbital of an atom to a vacant orbital of
the adjacent bonded atom.
• The extent of back bonding decreases with the increase in the size of the orbital participating
in bonding. Thus, the stability of the pi back bond will decrease accordingly.
• The relative stability of 𝛑-bond between various orbitals is given in the following order:
2p𝛑-2p𝛑 > 2p𝛑-3d𝛑 > 2p𝛑-3p𝛑 > 3p𝛑-3p𝛑
02

Conditions for back bonding

• It is formed after the formation of a sigma bond. For back bonding, it is necessary that a sigma
bond should already exist between the back bonding atoms in the species.
• For the pi bond formation, one necessary condition is that one element should be from the
second period and another one can be from either the second or the third period, in order to
have an effective overlap.
• One atom must have a lone pair and the other must have the vacant orbitals. However, these
two orbitals must have almost the same energy levels.
• There must be electronegativity difference between the atoms.
• The pi bond formed should be stable.

Predicting the existence of back bonding in compounds

Which of the following compounds will exhibit back bonding?

Solution

BF3
Boron and fluorine belong to the second period and therefore, there will be
effective overlapping and they can undergo back bonding. The electronic F
configuration of boron in its ground state and excited state are 1s2 2s2 2p1
and 1s2 2s1 2p2 respectively. Thus, boron has sp2 hybridization and it has one
unhybridized empty p-orbital. The electronic configuration of fluorine is 1s2 2s2 B
2p5. Three F atoms will form three sigma bonds with boron and result in a fully
filled configuration of the three F atoms. The back bonding takes place by the F F
donation of a lone pair of electrons from a fully filled 2p orbital of fluorine to an
empty 2p orbital of boron and this is denoted as 2p𝛑-2p𝛑 back bonding.

BCl3
Boron belongs to the second period and chlorine belongs to the third period.
The electronic configuration of boron in its ground state and excited state are CI
1s2 2s2 2p1 and 1s2 2s1 2p2 respectively. In BCl3, boron is sp2 hybridized and
hence, it has an unhybridized empty p-orbital. The electronic configuration of
chlorine is 1s2 2s2 2p6 3s2 3p5 . Three Cl atoms will form three sigma bonds B
with boron and result in a fully filled configuration of the three Cl atoms. The
back bonding takes place by the donation of a lone pair of electrons from a fully CI CI
filled 3p orbital of chlorine to an empty 2p orbital of boron and this is denoted
as 3p𝛑-2p𝛑 back bonding.

AlCl3 CI
In AlCl3, no back bonding exists as both Al and Cl belong to the third period.
Aluminium has empty 3p orbitals and chlorine has filled 3p orbitals. Since one
of the necessary conditions for back bonding of having at least one element Al
belonging to the second period is not followed, the back bonding is not possible
in AlCl3. CI CI
03

Cl3C+
The ground state electronic configuration of carbon is 1s2 2s2 2p2. The removal CI
of one electron from the ground state configuration gives C+ with 1s22s22p1
configuration. On excitation, the electronic configuration becomes 1s22s12p2.
Thus, carbon in the given structure is sp2 hybridized with one unhybridized CI C+
empty p-orbital. Three Cl atoms will form three sigma bonds with C and result
in a fully filled configuration of Cl atoms. The back bonding takes place by the
donation of a lone pair of electrons from a fully filled 3p orbital of chlorine to the CI
empty 2p orbital of carbon and this is denoted as 3p𝛑-2p𝛑 back bonding.

Cl3C-
The addition of one electron to the ground state configuration of carbon will CI
CI
give C - with 1s22s22p3 configuration. On excitation, the electronic configuration -
becomes 1s22s12p4. Three Cl atoms will form three sigma bonds with carbon C
and there is one lone pair of electrons present in the 2p orbital of carbon.
This will form a coordinate pi bond with the empty 3d orbital present in chlorine.
Hence, this compound will have 2p𝛑-3d𝛑 back bond. CI

Note

2pπ-3dπ back bond is more stable than 2pπ-3pπ back bond.

F3 C - -
Both carbon and fluorine belong to the second period and they have lone pairs C
of electrons. However, none of them have an empty p-orbital to accommodate F
F
the electron pair to form a pi coordinate bond. Hence, the back bonding is not
F
possible in this compound.

O(CH3)2
The excited state configuration of carbon is 1s22s12p3 that gives four sp3
hybridized orbitals. Among the four sp3 hybridized orbitals, one will form a
sigma bond with oxygen and the remaining three will form sigma bonds
with three hydrogen atoms. Here, oxygen is also sp3 hybridized (as it has O
two lone pairs and two sigma bonds that makes the steric number equal to H3C CH3
four and hence, sp3 hybridization). Even though both carbon and oxygen
are from the second period, they cannot form back bonds as neither
oxygen nor carbon have vacant orbitals that can accept electrons to
form the pi coordinate bonds.
PCl3 P
As phosphorus and chlorine belong to the third period, the necessary CI
condition for back bonding of having at least one element from the second CI
period is failed in PCl3 and hence, it will not have the back bonding. CI
04

CH3NCS
Nitrogen (of second period) has a lone pair that can make a pi coordinate bond. However, both
the carbon atoms surrounding the nitrogen atom cannot expand its tetravalency and they do not
have empty orbitals to accept the lone pair. Therefore, no back bond is formed in this compound.
As the nitrogen atom is surrounded by two sigma bonds and a lone pair, the steric number is 3
and the hybridization of N is sp2 that gives a trigonal planar geometry. So, the most appropriate
representation is structure (b).

N
H3C N C S C
CH3
S
(a) (b)
SiH3NCS
N (of second period) has a lone pair that can make a pi coordinate bond. Carbon cannot expand its
tetravalency and accept the lone pairs but the empty d-orbitals of Si (of the third period) can accept
the lone pair of nitrogen. Therefore, a 2pπ-3dπ back bond is formed. As the lone pair of nitrogen
is involved in back bonding, the steric number comes out to be 2 and hence, the hybridization of
nitrogen is sp and we see a linear shape.
H3Si N C S

NEET
Effects of Back Bonding

Affects the bond order and bond length

The very first condition of backbonding is that it is formed after the formation of a sigma bond.
Hence, back bonds have a partial double bond character. Therefore, bond order increases and
bond length decreases. The bond order is determined by the number of bonded electrons. The
higher the bond order, the stronger the pull between the two atoms and the shorter will be the
bond length.

Bond length ↓

Back bond is a partial

double bond

Bond order ↑

May or may not affect hybridization

In SiH3NCS, back bonding causes the hybridization of nitrogen to change from sp2 to sp as the
involvement of lone pairs of nitrogen in back bonding changes the steric number from 3 in
structure (b) to 2 in structure (a).
05

N
H3Si N C S H3Si C
S
(a) (b)
In BF3 , back bonding takes place by the donation of a lone pair from a fully F
filled 2p orbital of fluorine to an empty 2p orbital of boron and is known as 2p𝛑-
2p𝛑 back bonding. In BF3, hybridization does not change because of the back
bonding as the steric number of boron does not change. Thus, the hybridization B
of boron will remain sp2 even after the back bonding. F F

CI CI
In Cl3C-, the hybridization of C changes due to back bonding because the -
C
lone pair present in carbon is making a pi coordinate bond with the empty 3d
orbitals of Cl that causes the steric number of carbon to change from 4 to 3.
Hence, the hybridization of C changes from sp3 to sp2.
CI

Note

In BF3 and Cl3C-, all the three B-F and C-Cl bonds are equivalent in terms of the bond order and
bond length even after the formation of the back bond (due to resonance).

Predicting the change in bond angle due to back bonding

In which of the following does the bond angle around the central atom change due to back bonding?
(a) NBr3 (b) AsH3 (c) OCl2 (d) O(CH3)2

Solution

NBr3: Although N belongs to the second period, Br being a fourth period element will not cause
effective overlapping and hence, NBr3 will not have a back bonding.
AsH3: Since H does not have any lone pair or vacant orbitals, the back bonding is not possible. The
detailed discussion of AsH3 will be done under the topic of Drago’s rule.
OCl2: The lone pair of oxygen will form a pi coordinate bond with the empty 3d orbitals of chlorine
and will result in 2pπ-3dπ back bond. This will change the hybridization of O from sp3 to sp2 , which
gives an approximate bond angle of 120°.
Non-bonded electron pair repulsion (NBEPR) can be also stated as a reason that increases the
bond angle in this molecule. The repulsion between the non-bonded electron pairs of two Cl atoms
causes the repulsion between them and leads to an increase in the bond angle in Cl2O.
O(CH3)2: Though both carbon and oxygen are from the second period, they cannot form back
bonds as neither oxygen nor carbon have vacant orbitals that can accept a pair of electrons to
form the pi coordinate bonds. Hence, this compound will have no back bonding.
06

The steric repulsion caused by bulky CH3 groups will lead to an increase in the bond angle.
Hence, increase in bond angle is not because of back bonding but it is due to the steric repulsion
between the two bulky groups.
Hence, the bond angle around the central atom changes due to the back bonding in OCl2.
Hence, option (c) is the correct answer.

The back bonding will affect the Lewis acidic and basic nature of compounds.

Lewis acids Accept lone pairs of electrons

Lewis bases Donate lone pairs of electrons

When the lone pair of electrons are involved in back bonding, they are not available for donation
and hence, that compound will not exhibit the properties of a Lewis base. When the lone pairs
are not involved in the back bonding, they can be easily donated and that compound can act as
a Lewis base.
Similarly, when an empty orbital is less available due to its involvement in the back bonding, it is not
easily available for accepting the electrons. Hence, its Lewis acidic strength decreases. However,
when the empty orbitals are not involved in the back bonding, they can accept the electrons and
the compound can act as a Lewis acid.

Concept of back bonding

Which among the following statement(s) is/are not true?

(a) Trisilylamine is a planar molecule. (b) Trisilylamine acts as a Lewis base.
(c) Trimethylamine has a trigonal pyramidal shape. (d) Trimethylamine acts as a Lewis base.

Solution

Trisilylamine and trimethylamine are organic compounds and their structures can be given as
follows:
H3Si SiH3
N
N
CH3
H3C
SiH3 CH3

In trisilylamine, back bonding takes place as the lone pair of nitrogen can form a pi coordinate
bond with the empty 3d orbitals of silicon. Hence, 2pπ-3dπ back bond is present in trisilylamine.
Due to the involvement of the lone pair of nitrogen in back bonding, the hybridization of nitrogen
changes from sp3 to sp2 and the geometry changes to trigonal planar. Therefore, statement (a) is
true. Also due to back bonding, the lone pair of nitrogen is not available to be donated and will
reduce its Lewis basic nature. Thus, statement (b) is false.
07

In trimethylamine, carbon does not have empty d-orbitals to accept the lone pair of electrons from
nitrogen. Thus, no back bonding will take place in trimethylamine. Since the lone pair of nitrogen is
not involved in back bonding, the hybridization will remain sp3 with trigonal pyramidal shape. Due
to the absence of back bonding, the lone pair is available for donation and hence, trimethylamine
will act as a Lewis base. Thus, statements (c) and (d) are true.
Hence, the incorrect statement is option (b).

NEET
Drago’s Rule

The elements of the third and higher periods do not allow hybridization if they have lone pairs
along with low electronegative elements as the side atoms.
The three major conditions to be followed by a compound in order to follow Drago’s rule are as
follows:

Nitrogen family Oxygen family

• The central atoms should belong to
the third or higher periods. All the Nitrogen Oxygen
elements written in italics in the given
Phosphorus Sulphur
table will follow Drago’s rule. At this
level, we are not concerned about Arsenic Selenium
Drago’s compounds formed by bismuth
and polonium as they are radioactive. Antimony Tellurium
Bismuth Polonium
• The central atom should carry a lone pair.
• The side atoms with electronegativity less than or equal to 2.5 should be present in the
compound. At this level, we will consider the compounds with hydrogen as the side atoms.
Few examples of Drago’s compounds are PH3, AsH3, H2S, etc.

Consequence of Drago’s rule

111.0°
Comparison of bond angles in PH3 and NH3
Nitrogen in ammonia (NH3) is sp3 hybridized with a bond angle of 107°.
Nitrogen being a second period element will not obey Dragos’s rule. In
the case of phosphine (PH3), during its formation, the pure p-orbitals of P N
H
take part in bonding and avoid getting hybridized. The lone pair is present H
in the s-orbital which is stereochemically inactive (not participating in 107.9° H
hybridization). Phosphorus has three bond pairs and one lone pair. However,
the whole concept can be better explained with Drago’s rule. PH3 follows all 122.7°
the conditions of Drago’s rule and hence, it is a Drago’s compound. If we look
at its bond angle data, it shows that the p-orbitals have an angle close to 90°.
Looking at its Lewis structure, we can state that molecular geometry of PH3 is
P
trigonal pyramidal. H
H 93.5°
H
08

Important points to remember in PH3

• In PH3, hybridization does not take place.
• The pure p-orbitals of P take part in bonding.
• In phosphine, the orthogonal 3p orbitals overlap with 1s orbital of H.

Note

• SF6 is not a Drago’s compound. Although sulphur belongs to the third period, SF6 fails to
satisfy the second and third conditions of Drago’s rule, as the central atom does not have a
lone pair and the side atom fluorine has electronegativity greater than 2.5.
• As we move down the group, the size of the atom increases and the overlapping between the
central atom and the side atom decreases. This will result in the formation of a better Drago’s
compound and its bond angle will be closer to 90°.

Predicting the bond angle of a compound using Dragos’s rule

What is the bond angle in PH3 expected to be close to?

(a) 90° (b) 120° (c) 109° (d) 105°

Solution

Phosphine (PH3) is a Drago’s compound as it obeys Drago’s rule. In PH3, the

pure p-orbitals are involved in bonding. The lone pair is present in the s-orbital.
All the three p-orbitals (px, py and pz) are mutually perpendicular and thus, the P
bond angle θ is almost equal to 90°. H
Hence, option (a) is the correct answer. H 93.5°
H

Predicting the bond angles of compounds using Dragos’s rule

What is the correct order of bond angles in H2O, H2S, H2Se and H2Te?
(a) H2O > H2S > H2Se > H2Te (b) H2O < H2S < H2Se < H2Te
(c) H2O > H2Se > H2S > H2Te (d) H2O = H2S = H2Se = H2Te

Solution

Except H2O, all the other compounds will obey Drago’s rule. Hence, H2O will have the maximum
bond angle that is close to 104°. H2S, H2Se and H2Te will have bond angles around 90°. As we
move down the group, the size of the central atom increases and the overlapping between the
central atom and the side atom decreases. This will result in the formation of a better Drago’s
compound and its bond angle will be much closer to 90°. Thus, H2Te has the least bond angle
that is close to 90°. Hence, the bond angle follows the order H2O > H2S > H2Se > H2Te.
09

The bond angles of all the mentioned compounds are as follows:

H2O: 104°; H2S: 92°; H2Se: 91°; H2Te: 90°
Hence, option (a) is the correct answer.

NEET
Hybridization and the State of the Compound

Hybridization may differ with the state of the compound. Generally, the ionic compounds are
seen to be solids and the covalent compounds may exist in solid, liquid and gaseous states.
Certain compounds will change their hybridization with respect to their physical state. Some of
them are listed below.

PF5

PF5 is known to exist in its gaseous state (covalent form). The Ionic form of this compound is not
yet known. The steric number of phosphorus in PF5 is 5 and hence, phosphorus is sp3d hybridized.
Thus, PF5 has a trigonal bipyramidal geometry.

Compound Covalent (gaseous) Ionic (solid)

Form Hybridization Form Hybridization

PF5 (Only covalent
form) sp3d (Trigonal
PF5(g) Doesn't exist
bipyramidal

PCl5

PCl5 is known to exist in solid and gaseous state. In gaseous state, PCl5 has a steric number of 5.
Thus, the hybridization is sp3d with trigonal bipyramidal geometry. In solid state, it will dissociate
into its ions [PCl4]+ and [PCl6]-. P in [PCl4]+ has a steric number of 4 and thus, the hybridization is sp3
with a tetrahedral geometry. The steric number of P in [PCl6] - is 6 and hence, the hybridization is
sp3d2 with an octahedral geometry.

Compound Covalent (gaseous) Ionic (solid)

Form Hybridization Form Hybridization

PCl5 sp3d (Trigonal
PCl5(g) [PCl4]+ [PCl6]- sp3, sp3d2
bipyramidal)

PBr5

Both gaseous and solid forms of PBr5 are known to exist. In the gaseous form, it exists as PBr5.
The steric number of P in PBr5 is 5. Hence, the hybridization is sp3d hybridized with a trigonal
bipyramidal geometry. PBr5 in solid state exists as [PBr4]+ and [Br] -. The steric number of P in
[PBr4]+ is 4. Hence, the hybridization is sp3 with a tetrahedral geometry.
10

Compound Covalent (gaseous) Ionic (solid)

Form Hybridization Form Hybridization

PBr5 sp3d (Trigonal
PBr5 (g) [PBr4]+ [Br] - sp3 (Tetrahedral)
bipyramidal)

PI5

PI5 is known to exist in solid form only. The gaseous form of PI5 is very unstable due to five bulky
iodine atoms around phosphorus. In solid form, PI5 will dissociate into its constituent ions [PI4]+
and [I] -. The steric number of P in [PI4]+ is 4. Hence, the hybridization is sp3 with a tetrahedral
geometry.

Compound Covalent (gaseous) Ionic (solid)

Form Hybridization Form Hybridization

PI5 (Only ionic form) Doesn't exist. P can't accommodate
[PI4]+ [I] - sp3 (Tetrahedral)
five bulky iodine atoms

Note

For phosphorus halides, the change in hybridization with respect to their physical state can be
summarised as follows:

Phosphorus halide Covalent/Gaseous form Ionic/Solid form

PF5 PF5 (g) (sp3d) Does not exist

-
PCl5 PCl5 (g) (sp3d) [PCl4]+ [PCl6] . (sp3 and sp3d)
-
PBr5 PBr5 (g) (sp3d) [PBr4]+ [Br] (sp3)
-
PI5 Does not exist [PI4]+ [I] (sp3)

Table 1: Change in hybridization with physical state for phosphorus halides.

Cl2O6
O O
Both gaseous and solid forms of this compound are known. In the
gaseous state, it will exist as shown. Here, one Cl is connected to
O CI CI O
another Cl by a single bond. Each Cl is doubly-bonded to three O atoms.
Each Cl atom has a steric number of 4 and thus, the hybridization is sp3.
O O
11

In solid form, it exists as [ClO2]+ and [ClO4] -. Cl in [ClO2]+ has a steric number of 3 and hence, the
hybridization is sp2. Cl in [ClO4] - has a steric number of 4 and the hybridization is sp3.

Compound Covalent (gaseous) Ionic (solid)

Form Hybridization Form Hybridization

Cl2O6
Cl2O6 (g) sp3, sp3 [ClO2]+ [ClO4] - sp2, sp3

I2Cl6

In a covalent state, I2Cl6 will exist as a dimer with sp3d2 hybridization.

CI CI CI

I I

CI CI CI

In solid form, it exists as [ICl2]+ and [ICl4] -. The steric number of I in [ICl2]+ is 4 and the hybridization
is sp3. Thus, [ICl2]+ has a tetrahedral geometry. Due to the presence of two lone pairs, the shape of
[ICl2]+ becomes bent-shaped.

+
lp

lp
OR I+ OR I
I+
CI CI CI CI
CI CI

CI
I in [ICl4] - has a steric number equal to 6 and the hybridization is sp3d2. [ICl4] - will show an octahedral
geometry. The two lone pairs present in [ICl4] - will make the shape a square planar.

- lp
CI CI
CI CI
-
I I
CI CI
CI CI
lp
12

Compound Covalent (gaseous) Ionic (solid)

Form Hybridization Form Hybridization

l2CI6
I2Cl6 (g) sp3d2 [ICl2]+ [ICl4] - sp3, sp3d2

Mindful Questions from the Previous Session

• Find the hybridization of C in HCN.

• Find the bond angle between H-C-N.
• How many sigma and pi bonds are present in HCN?
The structure of HCN is given as follows:
H C N
• Hybridization of C in HCN
Carbon has formed one sigma bond with hydrogen and two pi and one sigma bonds with
nitrogen. Hence, carbon is sp hybridized. Nitrogen has formed two pi bonds and one sigma
bond with carbon and has a lone pair of electrons. So, nitrogen is also sp hybridized.
• Bond angle between H-C-N
Since both carbon and nitrogen are sp hybridized, HCN has a linear geometry and makes
the bond angle equal to 180°.
• Number of sigma and pi bonds present in HCN
There is one sigma bond present between carbon and hydrogen and one between carbon
and nitrogen. Also, there are two pi bonds formed between carbon and nitrogen.
Number of sigma bonds = 2
Number of pi bonds = 2

Mindful Questions for this Session

• What is inorganic benzene?

• How many back bonds are present in an inorganic benzene?

Summary

1. Back bonding: It is the transfer of a lone pair from a filled shell of an atom to a vacant orbital of
the adjacent bonded atom.
2. Effects of back bonding:
• Back bonding affects the bond order and bond length.
Back bonds have a partial double bond character. Therefore, the bond order increases and
the bond length decreases.
13

• Back bonding may or may not affect the hybridization.

In BF3 , the back bonding happens by the donation of a lone pair from a fully filled 2p orbital of
fluorine to an empty 2p orbital of boron and is known as 2p𝛑-2p𝛑 back bonding. In BF3 , the
hybridization does not change because of the back bonding as the steric number of boron
does not change. Thus, the hybridization of boron will remain sp2 even after the back bonding.
In CCl3-, the hybridization of C changes due to back bonding because the lone pair present
in carbon is making a pi coordinate bond with the empty 3d orbitals of Cl that causes the
steric number of carbon to change from 4 to 3. Hence, the hybridization of C changes from
sp3 to sp2 .
• Back bonding will affect the Lewis acidic and basic nature of compounds.
When the lone pair of electrons are involved in back bonding, they are not available
for donation and hence, that compound will not exhibit the properties of a Lewis base.
When the lone pairs are not involved in back bonding, they can be easily donated and that
compound can act as a Lewis base.
Similarly, when an empty orbital is involved in back bonding, it is not easily available for
accepting the electrons. Hence, the compound’s ability to exhibit the properties of a Lewis
acid decreases. However, if the empty orbital is not involved in back bonding, then it can
easily accept the electrons and the compound can act as a Lewis acid.
3. Drago’s rule: The elements of the third or higher periods do not allow hybridization if they
have lone pairs along with the side atoms whose electronegativity is ≤ 2.5.
The three major conditions to be followed by a compound in order to follow Drago’s rule are as
follows:
• The central atoms should belong to third or higher periods.
• The central atom should carry a lone pair.
• The side atoms with electronegativity less than or equal to 2.5 should be present in the
compound.
The hybridization may differ with the state of the compound. Generally, the ionic compounds are
seen to be solids and covalent compounds may exist in solid, liquid and gaseous states.
For phosphorus halides, the change in hybridization with respect to their physical states can be
summarised as follows:

Phosphorus halide Covalent/Gaseous form Ionic/Solid form

PF5 PF5 (g) (sp3d) Does not exist
PCl5 PCl5 (g) (sp3d) [PCl4]+ [PCl6]-. (sp3 and sp3d)
PBr5 PBr5 (g) (sp3d) [PBr4]+ [Br]- (sp3)
PI5 Does not exist [PI4]+ [I]- (sp3)