Lewis Acid - Lewis Base nit,

period
pitz? Asts1 a uB
EN

r
ceptor (etcrete "it> He? Hi:
Molecular Orbital Theory

Lewis Acid - Lewis Base Interaction Atomic orbitals combine to form Mo's

Anti-Bonding MO
(A t LB LA :B e- in BNO <
stability
* is
I
BF3 t
NHz IzB :NAy e- in ABNO 2

Ge- LB
Adduct stability

Types of Lewis Acid I Bond (nb na)

order=1

W
-

15
·

Hypovalent molecule (C-deficientspecies) 1S

H
nb no
=

ofe-present in BNO
H
Betz, BeClz, BE, AICly na= no
of e-present in ABM
I' Is
<4 3 (ye-) (6e7
-
(60-7
12
·
Metal Cations
-15
Bonding Mo
Mg2+, Nat, Alst, Int

Bo a
stability ofbond Stability -
No
a
·species having vacant d-orbital (species withcentral atom
belonging ~ Bond
strength
to 3rd period below)
or ~ Bond
Energy
L I

Comparison of Lewis Acidic Strength Bond length

· lewis
xe-deficiency - the os
ofcentral atom
Magnetic Behaviour
BeCIG
+2
CCly
+4
BEz
+3
Sich
+4
Y

Paramagnetic Diamagnetic
BE, Y
Silly BeCIa> CCly not a LA cunpaired e) (pairede-)
Y
· Lewis Acid 2 Er ofsurrounding atom -> All odd e-species 100- and let Paramagnetic
Exception:BF, <B11y <
BBs <
BIg (Due to back
bonding)
Comparison of Lewis Base Character
NO for no
ofc-<14
2 [7
size of
↳B a electron donation tendency (same group LB
 ~*
2Pz nex 14

a *cpu * 2py ~*
2Pz

a *cpu * 2py 1221

21
D ↓
2p Trick
·
2Pz

2p

jxzy
x 2 Px *2Py
2p

*
2s*

2 7
x

25 25
Trick 2121 Ne-x 14

is *is* 2s "est
0
25

%<pz (x2py xcpy) =

- Ys
(**2px x*2py) =
*
*2P2
BNO ABNO

t I -
t
r

1S · B
IS ⑧

ris
15
e
+ ye
overlap ve
-
overlap

-S
02:He-
8x2ee
=

2 -7 2121 ~15 -
is
s*
2 =7

is *is* 2s "est Fiz (F2n x2py) =

(12px x2py)
= -
2Pz (* px
*

x*py)
=

*22
=

(x24 xEy) *
2Pz
-
=

na)
30
1(1)
-

I(10 1) 2
=
=
= -

Trick
added in BMO OR is removed ABMO
·
If eis e- B0 + 0.5

↑
·

Ifeis added in ABMO or is removed from BMO B0 -

0.5
↑
sp hybridisation
82 (150) 02(14e-) 3.0
=

2.5
Cg.
=

02(17e) 02(180-)
1.5
= 1.0
=

stability & Bu

02's02 02 O
>
Bond
"
order: 02
Bond
length:OO:*** On 0 Eg. Becke

- Be
↑I
Hybridisation (Titue
honge) bonds bane hate unpair Krane

180

C - 12 I X
Ch B2 Ch

G.S 252
2p2 spsp

C -
1 1! ↑ sp2 hybridisation
Es 25
24
B
sp3 -> ↑W ↑

·
v1L * L ↑L 25 2p

↑ ↑ A -
1 H H H 25 2p
sp3
B I T ↑
Truck: Valid
only for species with
single central atom
sp2
Consider Fe's -> H F
Quotient bond pain
120B I
Total valence
e's in molecule
Trigonal Planar
F
Remainder ↑L
lone pair
2

2
Sp Linear &180 AV
12

120'
-
3 sp2 Trigonal Planar
sp3 hybridisation
CH4 I
ii. "
4
sp3 Tetrahedral 710928'
C
-
12

5
sp'd TBP
1203790
Es
! 10928"

in
or or or

.......................
M
I I i
6
sp3 d octahedral
sp3 -
72
F sp3d Pentagonal I Tetrahedral
(non-planar)
Bipyramidal
 sped hybridisation sp3ds hybridisation
PC15 (eqbond/xanial
P ↑L * * 4
I
F7
3d
GS

...--- -90
. .- .-.
-

- 2

i
4
-

- -
P -> Bonds can be assumed to be
formedbow the axis
---------.3d CL
35 --

,-3p.. anial so the orbitals withlobes

lying blow the anis will be
spd Cl

(stPutBy+day dazy)
used +

-
. . I 120 L P Ch ->
((,dzz)
sp3d Cl
equatorial
CL
Valence repulsion Theory (VSEPRT)
shell electron Pair

Acc, this different pairs present in the valence

to
theory the

p-canial" (P-(1) car shell of central atom exert repulsion over each other.
·
Repulsion blu different e-pairs follows the order
To minimise repulsion blue pairs of11 atoms the anial bond Ip-1px (p-bp bp-bp x

enternal and become

longer than equitorial. As no ofbond, repulsion o
·

(E) (=)> ( ) ( 3x(-) (-)

-
- = -
=

It is assumed to be
formed by the combination
of
°z ·
Ifthe molecules contain no lone pair and all the bonds are
Ch &
ofsame type then, it will have the same geometry
P ((s +

Px +
Py) as
produced by hybridisation
CL 2

de

If a molecule contains lone pair then its geometry

sp3d hybridisation will be different and bond
angle also
SFG
-____,#All positions are same in
eg. CH4
sp3 te
Hy0
sp3
- Co
geometry.
!
Bond Angle
reputsion
sp3d octahedral N

. . . . . . . . . .
Tetrahedral Pyramidal Bent-shape
i s+pn+ py+daryz 1070
LH -C-H 10928' (HNH= 104.59
KHOH=
............
=

Pz, d2
 Determination ofactual geometry (hir,
36p+1c.p
·

<H -
N-H 107
=

N
·
Determine the no. ofIp's and by's on the central atom

and calculate its

hybridisation. H H 4 up-bp repulsion, bond
angle yes.

·
Draw the same
geometry as
predicted by hybridisation. Trigonal Pyramidal
·
Place lone pair and multiple bonds at manimum
i repulsion
position. ·

2bp + 2lp
·
Do not consider the lone
pair in
shape, the
remaining Co
bent or
angular y-shaped
will be the actual shape ofmolecule
& H104.50
H
Ch

CL
is of H0 2 no. (sp) -> linear no. of
4) HO = 5
(sp3d) -
I
=

Ch P
2pp+0lp ->
BeCl, CO2 ·
5bp + olp non planar -
TBP
Ch
2) no of Ho =3 call positions are
equivalent)
36p 0lip eg:BC1s, Allly
· +
CL Ch

Ch B
Ch
·

4bp+4p (SFy)
·

2bp 1." Ip Az
F
S
·
r
--+ LFSF 790
I

A
1 (Bent eg. SO2
.
o F
F
I F

E
·

3bp+ 21.p Ch T-shape

F
120
B :
③

3) no
of10 =4(sp3) F
I

4bp lip CHy, CCly, Silly etc. 2bp+

· + 0
3P
·

H
Ion-planar) Tetrahedral XeFe -2 " linear (180) Planar
10928' "
C
I E

H
H -> sp3d F
F
+
·
6bp + 0lp -> SF6 S
F
F

F
 *s
⑳***I⑦
·

5bpt
↑
3.p Bis Bent rule can also be stated as

atom is attached to orbital

F F "If
a more EN an

Be square pyramidal it will decrease the %.S-character ofthe orbital"

E E

- S⑦④π?).
·

non-planar lone pair and multiple bonds always will be

① 2
present in
high orbitals y. with S-character.

4bp + 2
1.p I
·

F
Bond
Planar
Angle
-e
Square
F BA
x 1 Belly BC1Y CCly
F
repulsion s SY2 p3
not possible (180) (120) (109:28')
sip
·

Ifhyb same lone

31
pair -3

a ⑬ due to very
strong repulsion blw up-L.p and
1p x repl 2 I
BA
H20. NHy <CHy
up-bp, molecules does not exist
-

(ioz.) 1909.
2

· B 104

B
If hybridisation is same and up is also same

⑰
Bent Rule
2 %s-character
Electronegativity of an orbital
biff SA diff (A

EN
sp3 BA 2 size of SA

of
win
sp> sp2 x
atom
15 50% 33.33% 25% surv

~ 2

ja 0
will X
Greater the ys-character more closer be the orbital to nucleus ~ 2 - 2

are

and will its

higher electronegativity.
be H H
CH3 CH3
Bulky steric hindrance
Acc. to Bent Rule for a molecule in which
surrounding atoms are

bonded
throughsingle bonds. The element
having more
electronegativity
will bond
preferably withorbitals
having lows character (low EN) H20 U20 AD
(120 x FzO Y H2O
Valence Bond Theory INA Inter- nucleic Anis

long
Attraction
Range fora teeof sen Anis passing through the nucleus.

Repulsion
shape and orientation ofatomic orbitals
H..........
--
H

H ............
H s-orbital: spherically symmetrical
H
--------
H

CA
-

&B I t
5

Attractive force Repulsive

I force
These not
t are
charges,
NA NB NA- eB NA- NB these are
signs ofwave function
NA-CA CA eB
A B B -

p-orbital
AB -
attraction dominates dumb-bell shape bothlobes have opposite sign ofwave function

nodal
dominates
C
Up B) -

Repulsion pu, py, P2 z

at pt B:Attraction -
Repulsion il ↓ ↓
uZ
B yz my plane
↓
nodal
plane
Concept ofoverlapping
The penetration of atomic orbitals oftwo atoms into each other plane in "whichprobability
e-wave nature wave
function(4) of finding - is zero. 42=0

Bond formationblu two atoms

-

+ occurs
by overlapping of atomic ↓-orbitals
orbitals ·
double dumb-bell

As result of having unpaired functions.

e-each
samesign
have
a -> one ·

opposite lobes of wave

overlapping the
e-density will become -> one vacant orbital and one
fully-
manimum bow the two bondednuclei filled orbital.

>
 Types of Overlapping
1) Anial/Head on
overlapping
ercloud
·
When the orbitals overlap withtheir
lying along the intermolecular
anis.

·--bond are
formed due to anial
overlapping.
 As p-orbitals are
directionally more concentrated

(i.e lobes lie in a certain direction) so the

overlapping
extentwill be
higher
shell
esseplup Y For same

For differentshells -> As the shell number increases size

oforbital
also res.

orbitals increases, the internuclear

Is <25 < 3s..... As the size of
2p<bp
<
up...... distances also yes and hence overlapping becomes less

effective

15-25 23-25
x
Y 35-25

Is-Is 23-25 y 35-35

Is-2py 1s-3p X 15-4p

3p-3pX
sp-2px up-up

comparison of 5and a bondstrength

bond
comparison ofand a
strength
Entent
strength of 2 ofoverlapping
boud ⑳

comparison
S-S
oft-bonds
s
-p p p
-
68 - Y

D Inter-nuclear repulsion
⑦ S
 Fajan's Rule Application
to compounds is 100% conic or 100% covalent non-polar Mnet 0
=

② polar Met FO
cation
· covalentnature &
charge on

· covalent nature a ·
If in a molecule all bonds are same and the
size
ofcation molecule does not contain lone pair.
Polarising power & Covalent( Unet= o
·

CL
Cl

Ch
C114 B
C
CL
CL
CL B(ly Unet 0
=

Cl

Becky, P115, B11s, CCly, SEg Muet=0

or diff
If the molecule contains
up types ofbond then
Met may or may not be zero

302 i 1 CD
S O

H H

Mnet FO Unet FO
Lit Nat xkt Polar Polar

Lit (Nat
<Ng2+
Fajan's Rule CovalentCharacter

lill*MgCl< AIC,
d
Dipole Moment(U) I
-

distance q
u qxd
= -
> q

↳
Charge Representation - Cl
Less EN
Unit:Debye 1D 3.33 x
= 10-30 (m EN move

EN Y ENH
 H
CL 20 -

Co
-
Polar
Ch
Unet FO
lattice Energy
ionic lattice
Energy required, when I mole
of
an is formed from its constituentions.

Nat
(g) (g) NaCl (s)
-

+
(1

Energy required
↓
1. E

largee
Ifa

LiCk<NgCy AICIs