P Block

BACK BONDING
F
e–deficient species
B
F F
B–F bond length is less than expected but bond energy & bond strength are
more than expected in BF3 molecule and it can be explained by back bonding.
Conditions of B.B. -
1. Both covalently bonded atoms must belongs to 2nd period.
OR
1 atom belongs to 2 period and the other atom belongs to 3rd period.
nd

2. 1 covalently bonded atom must have lone pair and the other atom
must have vacant orbital (V.O)
 BACK BONDING
Effects of B.B -
Ex : B – 2s2 2P1
1. Bond length decreases.
G.S. –
2. Hybridisation may change ES1 –
3. Bond angle may change s s s
F F F
4. Geometry may change
5. Acidic and basic nature of molecule F
B F
F
pp - pp p
F F F
s B B F B F
s F F F
F s
2p 2p 4 = 1.33
B.O = —
F 3
(V.O) (L.P) B F
F
Note - Back bond is a type of p Co-ordinate bond.
 BACK BONDING
• Bond bonding is a type of sideway overlapping in which there is a slight
transfer of e– from e– rich species to e– deficient atom.

• As a result the e– deficiency of e– deficient atom gets slightly compensated

so BF3 do not form dimer.

• In BF3 molecule there is no change in hybridisation, geometry, shape

and bond angle but bond length decreases.

Extent of B.B -

2p–2p > 2p – 3p > 2p – 4p > 2p – 5p

Ex : BF3 > BCl3 > BBr3 > BI3

 BACK BONDING
Q. Compare Bond Length, Bond Strength, Bond Energy Bond Order,
Hybridisation and % s-character.
BF3 BF4– (BF3 + F – )
–
F
F F
B F B.B B F B.B
F F
4
B.O = 1.33 3 B.O = 1

B. Strength / B. Energy -
B. Length -
Hybridisation - sp2 sp3
% s-character - 33.3% 25%
Bond Angle -
Geometry - Trigonal planar Tetrahedral
 BACK BONDING
Q. Compare Lewis Basic Strength Between Trimethyl Amine & Trisilyl Amine.

N(CH3)3 N(SiH3)3
(Trimethyl amine) (Trisilyl amine)
..
N H3Si ..
N SiH3
CH3 CH H3Si
CH3 3
(pp - dp)

Hybridisation - 3s + 1LP = 4 = sp3 3s + 0LP = 3 = sp2

Geometry - Tetrahedral Trigonal planar
Shape - Pyramidal Trigonal planar
Trimethyl amine is a better Lewis base than Trisilyl amine because lone pair is
free to donate in trimethyl amine but lone pair is busy in trisilyl amine in B.B.
 BACK BONDING
Applications of Back Bonding :

1. Back Bonding explains the abnormal bond length, bond energy, bond

strength of B-F bond in BF3.

Q. In which of the following B-F bond length is minimum.

(1) BF4– (2) BF3

(3) BF3  NH3 (4) All B-F Bond Lengths are same

Ans. (2)
 BACK BONDING
2. Back Bonding explains the Lewis acidic nature of molecules :

(i) BF3 BCl3 BBr3 BI3

2p-2p 2p-3p 2p-4p 2p-5p

Size of B.B. e-deficiency L.P. accepting L. Acidic

orbital of Boron tendency nature

(ii) BeF2 BeCl2 BeBr2 BeI2

2p-2p 2p-3p 2p-4p 2p-5p

Size of B.B. e-deficiency L.P. accepting L. Acidic

orbital of Boron tendency nature