Electronic Effects on the Strength of Group 13 Acids

Acidity

BF3 < BCl3 < BBr3 ~ BI3

Reason: π-donation from halide

F > Cl > Br, I
B-X interaction: B-F > B-Cl > B-Br ~ B-I

B
B
F
F
F

F F F

B B B
F F F F F F
 Question
1/.Replacing F with Me (CH3) leads to a series of
decreasing adduct stability: BF3 > BF2Me > BFMe2 ~
BMe3 when NMe3 is the donor. Why?

2/. The order of acidity wrt NMe3 is AlMe3 > GaMe3 >
InMe3. Why?
 Examples of Lewis Acids: Group 14
Group 14 elements (except carbon) can accept electron pairs by using
their empty d-orbitals

CH3 F -
CH3
Sn + F- H 3C Sn
Cl
H3C CH3 CH3
Cl
F F
-
+ F
Si F- F Si
F
F F
F
F
 Examples of Lewis Acids: Group 15
This family affords many common examples of Lewis
bases and a few less widely appreciate Lewis acids

e.g. PCl5 is a monomer in gas phase but an ionic compound in solid state

Cl Cl Cl
Cl Cl Cl
Cl P P P
Cl Cl Cl Cl Cl
Cl Cl Cl

Gas phase Solid State

 Examples of Lewis Acids: Group 15

F F
F
F F
F Sb + F Br Br
F Sb F
F F F
F
F F F
 Examples of Lewis Acids: Group 16
Most of the group 16 compounds are Lewis base but
there are few examples of Group 16 Lewis acids

SO3 is a strong acid towards donors such as amines,

alcohols

O O
+ NR3 R 3N S
S O
O O O
 Examples of Lewis Acids: Group 16

F F
F
F
S + -
+ R4N F R4N+ S F
F F
F F

Question
It is known that dissolving SO3 in water leads to
sulfuric acid. Could you express the reaction in
term of an acid-base reaction between SO3 and
water?
 Examples of Lewis Acids: Group 17

I I + I- I I I
-
triodide ion

I Cl + Cl- Cl I Cl
-
Cl
Cl Cl
-
I Cl + Cl- I
Cl Cl
Cl
 Question
Give the geometry of I3- and I3+ ions by using
VSEPR theory

Examples of Lewis Acids: Group 18

XeF6 + F- → [XeF7]-

XeO3 + F- → [XeO3F]-
Structures of Some Lewis Bases: Group 14
R = alkyl, aryl group or H

anionic
-
R
R Alkyl ion
C

H H -
Example of aryl ion:
H phenyl ion

H H
Structures of Some Lewis Bases: Group 15
R = alkyl, aryl group or H
Neutral
Anionic
-R R
R
N amide N amine
R
R

R
- R

P phosphide R phosphine
R P

R
-R arsenide
R
arsine
R
As As
R
R
sp3 hybdridization sp3 hybdridization
 Structures of Some Lewis Bases: Group 16

dianionic anionic neutral

- H2O
O H hydroxide
O2- oxide - H-OR alcohol
O R alkoxide R-O-R ether
-
S R H-SR thiol, H2S
S2- sulfide - thiolate
S H R-S-R thioether
hydrogen
- sulfide
Se R H-SeR selenol, H2Se
Se2- selenide selenoate
- hydrogen
selenide
Se H R-Se-R
dialkylselenider
R = alkyl group i.e. CH3

Group 17 – halides are common Lewis bases

Structures of Some Lewis Bases:
pseduohalides

- + -
N N N Azide ion

-C N Cyanide ion

- -
S C N S C N Thiocyanide ion

- -
O C N O C N Isocyanate ion
Structures of Some Lewis Bases:
Heterocyclics

N O
pyridine furan

N S
pyrrole thiophene
H
Structures of Some Lewis Bases Containing
> 1 Donor Atoms

H2C CH2 O-
C O
H2N NH2 N
O O

ethylenediamine (en) nitrate ion carbon monoxide

O-
O O -
C C C S C N
O O O O-
oxalate ion carbonate ion thiocyanide ion
 Factors that Control Lewis Basicity

Electronic effect

NF3 < NH3 < NMe3

Reason: F is more electron withdrawing than H and Me

Me is electron donating
 Question
1/. Identify the donor atoms in the following compounds

(i) (CH3)2SO (ii) SnCl2 (iii) SO2

2/. Interpret the order of adduct stability of the

following bases with BMe3

NH3 < MeNH2 < Me3N < Me2NH

Me = methyl group CH3

Question
1/. What Should be the order of basicity of the following
pyridines with respect to BMe3?
CH3

N N CH3 N

2/. Account for the basicity order of the oxygen atoms

in the following molecules
Me Me Me
C O C O > C O
>
Me2N Me MeO

Me = methyl group CH3