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3.6 Valence Shell Electron Pair Repulsion (VSEPR) Theory 75

pair will occupy a stereochemically inactive s orbital, and the bonding will be through p orbitals, and bond
angles will be nearly 90° if the electronegativity of the surrounding atom is £ 2.5.
The above rule is based upon the relation between hybridization and bond angle for two or more
equivalent s–p hybrid orbitals, where the fraction of s character (S) or fraction of p character (P) is given
by the relationship:
S P -1
cos q = = (for 90° < q < 180°)
S -1 P
For example, for AsH , H ! As H angle is 91.8°, and from calculation it can be shown that each As–H bond
3
consists of almost 97% p character and 3% s character. Hence, it can be concluded that there is no hybrid-
ization or the extent of hybridization is very less for PH3, AsH3, SbH3, H2S, H2Se and H2Te molecules.
The cause for no hybridization in these molecules can be explained as follows. In case of P, the energy
required for hybridization is about 600 kJ mol–1 which is not compensated by the energy released from the
bond formation using hybrid orbitals. From the energy point of view alone, the most stable arrangement
would be utilizing pure p orbitals in bonding with the lone pair ‘sinking’ into a pure s orbital.
Based upon the above discussion, we can explain the following facts.
a. PH3 has much lower solubility in water as compared to that of NH3.
b. The formation of PH4+ is difficult as compared to that of NH4+ which is supported by the fact that
NH 3 + H 2 O ! NH 4 + + OH -
whereas,
Æ PH 4+ + OH -
PH 3 + H 2 O æ¥æ
The reason for the above observation is that the amount of [H+] is quantitatively less to protonate the lone
pair that resides at almost pure s orbital in case of PH3. When [H+] increases in the presence of strong acids
like HX (X = Cl, Br and I), PH4+ is formed more readily.
PH 3 + HX ® PH 4+ + X-
3. The complexing ability of NH3 is much higher as compared to that of PH3.
These three observations can be explained on the basis that the lone pair donating ability for P in case of
PH3 is much less because the lone pair resides at almost pure s orbital. In case of NH3, the lone pair is pres-
ent in one sp3 hybrid orbital and can be donated easily.

Back bonding
The phenomenon of back bonding involves transfer of lone pair from filled shell of an atom to the unfilled
shell of the adjacent bonded atom.
It is a kind of coordinate p bonding which may be partial or full, depending on the relative donating
and accepting ability of the donor and accepter atoms. In general, the donor atoms are the second period
elements carrying lone pairs, such as F, O, N, C; sometimes Cl, Br, I, P, S can also act as donor atoms depend-
ing on circumstance.
1. Back bonding with F as donor atom
a. Considering the electronegativity of the surrounding atoms, the expected bond angle order for PH3
and PF3 is PH3 > PF3. But in reality, it is PH3 < PF3. This is due to back bonding in PF3 which is shown
in Figure 3.11.
- - - -
P P P P
+F F F F
F F+
F +F F F F
F
Resonance hybrid
Figure 3.11 Back bonding in PF3
Hence, due to back bonding the partial double bond character develops in a bond causing a decrease
in the bond length; the bond angle may or may not increase, but it never decreases.
Hence, the following bond angles observed are well explained.

PH3 and PF3 AsH3 and AsF3

93.8° and 97.8° 91.8 ° and 96.2°
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76 Chapter 3 Chemical Bonding

b. In case of BF3, the extent of back bonding is more than that observed in PF3 F
d+
because of the 2 pp - 2 pp overlap in case of BF3, while that in P–F bond is
3dp - 2 pp . However, there is no change in the bond angle due to absence of the 120° 120°
lone pair on the central atom. B-
d+ d+
Hence, it is also clear that dB – F in BF3 is less than that in BF4– because back bonding F F
is not possible in BF4– due the non-availability of vacant orbital in B atom under sp3 120°
hybridization.
2. Back bonding with O as donor atom
a. The expected bond angle order for H2O, Cl2O and + +
O + O d-
F2O is H2O > Cl2O > F2O based on the electro- O Cl - d- Cl
-
Cl Cl Cl
negativities of the surrounding atoms. But in real- Cl 110°8°
ity, the order is Cl2O (110°8′) > H2O (104°5′) > F2O Resonance
hybrid
(103°2′). This is also explained on the basis of back
bonding in Cl2O (Figure 3.12), which is not pos- Figure 3.12 Back bonding in Cl2O
sible in H2O and F2O.
For the analogous compound SCl2, the bond angle is 102° since the lone pair of S or Cl atoms need not
be delocalised due to the availability of vacant d orbitals of their own.
b. The dB–O in B(OH)3 < dB–O in [B(OH)4]–. This is because back bonding is possible in case of B(OH)3
from O atom to vacant p orbital of B atom, which is not available in case of [B(OH)4]– and hence no
back bonding is possible.
c. (CH3)2O forms a complex with BF3 easily, while (SiH3)2O O O
cannot do so because the availability of the lone pair on O atom H3C 110° CH3 H3 Si 144° SiH3
decreases due to back bonding from O atom to vacant 3d orbital (a)
of Si atom. C atom has no such vacant orbital for back bonding. O O
and
In case of (CH3)2O, the positive deviation of the bond angle Cl 110°8¢ Cl H3Si 144° SiH3
(b)
with respect to hybridization can be explained on the basis of
steric crowding of two methyl groups. In case of (SiH3)2O, the Figure 3.13 Bond angle devia-
huge bond angle increase is mainly due to back bonding and tion in (a) (CH ) O and (SiH ) O.
3 2 3 2
partly due to steric repulsion (Figure 3.13a). (b) Cl2O and (SiH3)2O.
If we consider the bond angles of Cl2O and (SiH3)2O, in both
the cases 3dp-2pp type of back bonding takes place but the huge angle change in case of (SiH3)2O is due to
the much higher extent of back bonding as compared to Cl2O. This is because of the presence of three lone
pairs on each Cl atom which retard the flow of electrons
from O atom. This phenomenon is not observed in case of O- O-
(SiH3)2O due to absence of lone pairs. (Figure 3.13b). B B
-
d. The boroxine (B3O6) ring is planar due to back bonding O O O+ +O
and it is aromatic in nature (Figure 3.14). Here the back
bond is considered as a full coordinate p bond in a par- -
B B B -B O-
+
ticular resonating structure according to the bond order O O O -
O- O
-
observed. Similarly B3N3H6 is also planar and aromatic -
due to back bonding. Figure 3.14 Structure of [B3O6]3 ion.
+
e. In C ∫ O molecule also, the coordinate p bond may be considered as back bond from O atom to C
atom. The structure before back bonding may be written as : C = O: !! In this arrangement the lone pair
from O atom is donated to the vacant orbital of electron !!
F3C O CF3
deficient C atom. Al Al
f. In (F3C)2 Al – O – Al(CF3)2, the AlOAl! angle is almost 180° CF3
CF3
(i.e. 178°) so the Al – O – Al skeleton is almost linear, and oxygen 178°
atom may be considered as sp hybridized (Figure 3.15).
Here the extent of back bonding is enhanced by the Figure 3.15 Structure of
inductive effect of strongly electronegative CF3 group which (F 3C)2 Al – O – Al(CF3)2.

increases the electron deficiency of Al atom that is already electron deficient due to incomplete octet.
Another example of the compound where the O atom is sp hybridized is Ph3Si–O–SiPh3 in which
! angle is 180°.
the SiOSi
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3.6 Valence Shell Electron Pair Repulsion (VSEPR) Theory 77

g. R3Si – O – H is more acidic than R3C – O – H. This is also due to back bonding from O atom to Si
atom which increases the polarity of O – H bond and stabilizes the conjugate base R 3 Si - O.
-
R3Si O H or R3Si O
(3d) (2p) (3d) (2p)
! > COH
This also explains the bond angle order of SiOH ! in the above compounds.
h. R3NO has a higher dipole moment as compared to R3PO due to back bonding from O atom to
P atom though the electronegativity difference between P and O is much larger as compared to that
between N and O.
+ + .. ..
R3 N ¾ O ; R3 P ¾ O : « ¾¾
R3P ¬ ¾
®O:
¾
.. ..

( m = 5.0D) m = 4.37 D (3d)

(2 p).
i. The 2pp − 2pp back bonding in B(OH)3 or B(OMe)3 explains why the BOH ! and BOC ! angles are 112°
and 113° respectively.
3. Back bonding with N as donor atom
a. The bond angle order is NCl 3 (107°45¢) > NH 3 (107°) > NF3 (102°).
This is due to very slight back bonding in NCl3 from 2p orbital of N to 3d orbital of Cl the extent of
which is very less because only one lone pair is distributed over three chlorine atoms.
b. B3N3H6 is planar and aromatic due to back bonding from N to B atom in the form of 2pp − 2pp.
c. (CH3)3N is pyramidal while (H3Si)3N is planar, and similarly (SiH3)3P is pyramidal and (GeH3)3N
is planar. This can be explained on the basis of back bonding. In case of (CH3)3N, there is no back
bonding, however 2pp - 3dp and 2pp - 4dp back bonding in (SiH3)3N and (GeH3)3N respectively
makes them planar and N atom is forced to adopt sp2 hybridization. In case of P(SiH3)3, the inter-
nuclear distance is large and P atom has its own vacant d orbital. Hence the tendency to donate
lone pair is very less and it adopts pyramidal structure and P atom is sp3 hybridized.
It is also observed that (CH3)3N is more basic as compared to (SiH3)3N due to the same reason
and they behave differently towards HCl.
(CH 3 )3 N + HCl Æ (CH 3 )3 NH+ Cl - (Lewis acid-base adduct)
(SiH 3 )3 N + 4HCl Æ NH 4 Cl + 3SiH 3 Cl (bond cleavage through SN2 mechanism)
d. H3C – NCS is bent while SiH3 – NCS is linear.
In CH3NCS there is no back bonding, while in SiH3 – NCS the extent of back bonding (2pp - 3dp)
is so large that Si – N – C – S skeleton becomes linear.
Similarly, in analogous series, CH3 – NCO is bent and H3Si – NCO is linear but H3Ge – NCO is
again bent. Here back bonding (2pp – 4dp) is relatively ineffective as compared to (2pp - 3dp) in
H3Si – NCO and cannot stretch the angle up to 180°. Hence H3Ge – NCO is angular.
In contrast, it is notable that (SiH3)3N and (GeH3)3N are planar while H3Si – NCO is linear but
GeH3 – NCO is bent. Back bonding occurs in both (GeH3)3N and H3Ge – NCO and is 2pp - 4dp.
The back bonding extent is enough to increase the bond angle from 109° 28′ to 120° in case of
(GeH3)3N but not enough to increase the bond angle from 120° to 180° in case of H3Ge – NCO.
! angle in CH NCS is 142° while HNN
Note: It is interesting to note that CNC ! angle in HN is
3 3
112°, though they have identical skeleton. This can be explained with the help of resonance hybrid
structures shown in Figure 3.16.
The contribution of structure (III) is negligible because the p bonds between C and S, i.e., 2pp – 3pp
are ineffective and the resonance hybrid structure is contributed by structures (I) and (II). Hence
the bond angle is in between 120° and 180°, i.e., 142°.
142°
H3C - + CH3
H3C N-C S N C S
+ - N C S
H3C N C-S
(I) (II) sp 3 (III) Resonance
sp sp 2 hybrid

Figure 3.16 Resonating structures for CH3NCS.

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78 Chapter 3 Chemical Bonding

In case of HN3, the resonating structures are as shown in Figure 3.17.

H + - H - + H 112°
+ + N N N N N N
H N N N2- N
N N
sp sp 3
sp 2 Resonance
(I) (II) (III)
hybrid

Figure 3.17 Resonating structures for HN3.

Here the contribution of structure (I) is very less. The hybrid structure is contributed largely by struc-
tures (II) and (III). Hence the bond angle is in between 109° 28′ and 120°, i.e. 112°.
e. The bond length order of the B–N bond in the following compounds is

B(NR 2 )3 > HB(NR 2 )2 > H 2 B - NR 2

and the order of energy required for the rotation of the B – N bond is just reverse, i.e.

B(NR 2 )3 < HB(NR 2 )2 < H 2 B - NR 2

Here back bonding from N to B is most restricted in case of B(NR2)3 due to steric crowding and most
relaxed in case of H2B – NR2. Hence, the above orders are well explained.
4. Back bonding with C as donor atom
a. CHCl3 is more acidic than CHF3 which is explained as follows:
-
CHCl 3 ! H + + C Cl 3
-
CHF3 ! H + + C F3

C C
Cl Cl F
F
Cl F

The lone pair on C atom gets delocalized through 2pp – 3dp bonding in Cl 3C - , which is not possible in
case of F3 C - .
- -
b. R 3C is pyramidal while (CN )3C is planar due to the back bonding from the lone pair of C atom into
the p * orbital of the C ∫ N group.
5. Back bonding with halogens (Cl, Br, I) as donor atom
a. The Lewis acidity order of BX3 molecules is explained in terms of back donation from X atom
(X = F, Cl, Br, I) to B atom. The back donation ability order for halogens towards B atom is
F >> Cl > Br > I. This is because
(i) the size increases and mismatch of the over-
lapping orbital increases down the group, i.e. Cl
from F (2pp – 2pp) to I (2pp – 5pp).
O S B
(ii) F atom is a good donor due to its filled shell,
Cl 110°8¢ Cl Cl 102° Cl Cl Cl
while in general Cl, Br, I do not like to act as
donor atoms; only act as donor atom when 2pp – 3dp No such 2pp – 3pp
the adjacent atom is electrons deficient due 'back bonding'
to incomplete octet like B atom as shown in
Figure 3.18 Effect of back bonding of halogen
Figure 3.18.
on Lewis acidity.
Finally the Lewis acidity order is:
BF3 < BCl 3 < BBr3 < BI 3 .
b. The relative stability order for the diradicals is
: CH 2 < : CCl 2 < : CF2
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3.7 The Extent of d Orbital Participation in Molecular Bonding 79

Here C atom is electron deficient due to incomplete

C C
octet and no back bonding is possible in :CH2, Cl (3d)
Cl Cl Cl
while 2pp – 2pp and 2pp – 3pp kind of back dona- Cl
tion takes place in :CF2 and :CCl2 respectively. Since 2pp – 3dp 3pp – 2pp
the 2pp – 2pp back donation is most effective, :CF2 -
is more stable as compared to :CCl2 and :CH2. Figure 3.19 Back bonding in CCl3 and :CCl2
Note: An interesting phenomenon- observed is that
the direction of back bonding in CCl 3 and :CCl2 is just reverse (Figure 3.19).

3.7 | THE EXTENT OF d ORBITAL PARTICIPATION IN MOLECULAR

BONDING
The bonding in PCl5 may be described using hybrids of the 3s, 3p and 3d atomic orbitals for Ρ – see
below. However, there are doubts as to whether d orbitals can take part and this has led to the decline
of valence bond theory.
3s 3p 3d
Electronic structure of full
phosphorus atom – inner
ground state shell

Phosphorus atom –
excited state
Phosphorus having gained five
electrons from chlorine atoms
in PCl5 molecule
sp3d hybridization, trigonal bipyramid

However, d orbitals are in general too large and too high in energy to mix completely with s and
p orbitals. The difference in size is illustrated by the mean values for the radial distance for different
phosphorus orbitals: 3s = 0.47 Å, 3p = 0.55 Å and 3d = 2.4 Å. The energy of an orbital is proportional
to its mean radial distance, and since the 3d orbital is much larger it is much higher in energy than the
3s and 3p orbitals. It would at first seem unlikely that hybridization involving s, p and d orbitals could
possibly occur.
Several factors affect the size of orbitals. The most important is the charge on the atom. If the atom
carries a formal positive charge then all the electrons will be pulled in towards the nucleus. The effect is
greatest for the outer electrons. If the central Ρ atom is bonded to a highly electronegative element such as
F, Ο or Cl, then the electronegative element attracts more than its share of the bonding electrons and the
F or Cl atom attains a d– charge. This leaves a d+ charge on Ρ, which makes the orbitals contract. Since the
3d orbital contracts in size very much more than the 3s and 3p orbitals, the energies of the 3s, 3p and 3d
orbitals may become close enough to allow hybridization to occur in PCl5. Hydrogen does not cause this
large contraction, so PH5 does not exist.
In a similar way the structure of SF6 can be described by mixing the 3s, three 3p and two 3d orbitals,
that is sp3d2 hybridization.
3s 3p 3d
Electronic structure of full
sulphur atom – ground inner
state shell

Electronic structure of
sulphur atom – excited
state

Sulphur atom having gained

six electrons form fluorine
atoms in SF6 molecule
sp3d 2 hybridization, octahedral structure

The presence of six highly electronegative F atoms causes a large contraction of the d orbitals, and lowers
their energy, so mixing may be possible.