Structural Effects

T electron delocalization (Resonance)

CH 2 .. CH Cl : ..
.. O C .. .. NH 2 .. NH2

.. Cl : ..

:O: CH 3 C .. O H ..

Structural Effects
T electron delocalization (Resonance)

Structural Effects
T electron delocalization (Resonance)

Structural Effects
T electron delocalization (Resonance)

:O:
:O:

.. :O

.. :O:
+

..
2

Hyperconjugation

Structural Effects
H H C CH CH 2 H

..H C CH CH2 H

..H C CH CH 2
+

H H

..H C CH CH2 H
+

Structural Effects
Hyperconjugation

Dienes

CH2

CH CH CH2

cumulative

conjugated

isolated

Structural Effects
Hyperconjugation
H H C H
-

H H C H ..

H H C H

..
-

Structural Effects
Hyperconjugation
H H C C H H
H H C C H H
-

Structural Effects
+ 3 3 + + + 3 3 3

O N

Inductive Effect

Structural Effects

Electron attracting inductive with excess effect positive charges

R N R R those with electronegative atoms F NH2 OH OCH Cl Br
+ +

NH

NO2

groups exhibiting orbital electronegativity C N N N

those with easily polarizable valence electrons I

-

Inductive Effect

Structural Effects

Electron attracting inductive effect H H

H3
H H3 H H2 H Cl
CH 3

l
H CH2 H

H

CH3 H3C N CH3

+

--

Inductive Effect

Structural Effects

Electron repelling inductive alkyl r s effect

CH 3 negati e gr COO
-

s S
-

O H3C C O
--

H 3C

H 3C CH C N H 3C

O R C O C

O O O
R

O S O O

Steric Effect

Structural Effects

Hydrogen Bonding
F O H H H H F O

Structural Effects
H H
H H

H H

H

H O H R H O O H H O R H

O F

H
OH OH

O H O R C O H O C R

H C O O H

Acids and Bases

BrnstedLowry Acids and Bases

 An acid is a proton donor  A base is a proton acceptor
HBr + H 2O Br + H 3O

acid

base
NH4 + OH

NH3 + H2O base acid

Note that water can act as an acid or a base

Acids and Bases

BrnstedLowry Acids and Bases

HBr + H 2O Br + H 3O

HBr acid

H base

Br

H H conjugate acid

conjugate base

Every acidbase reaction involving proton transfer has two conjugate acidbase pairs.

Acids and Bases

Lewis Acids and Bases

 A Lewis acid is an electron pair acceptor.
(think empty orbital)

 A Lewis base is an electron pair donor.

(think filled orbital) The result of a Lewis acidbase reaction is often called an adduct.

Acids and Bases

Lewis Acids and Bases

H + O
O H H

Lewis acid Electron deficient

Lewis base Electron rich

Adduct New covalent bond

Acids and Bases

Lewis Acids and Bases

Examples of Lewis Acids: Fe3+ AlCl3 Examples of Lewis Bases:
H3 H2O Cl


H3 O+

Acids and Bases

Acids and Bases

 pH = log[H3O+]
HA + H2O A + H 3O

A Ka =

H O
HA

pKa = log (Ka)

Acids and Bases

Acid Strength
HA + H2O H O+ +
A
E N E R G Y

A-

WEAK ACID Has a strong conj. base (@higher energy) STRONG ACID Has a weak conj. base (@lower energy)

A HA
ionization easier

Acids and Bases

Acids and Bases

Acid Strength
 Factors that influence stability of the conjugate base include:
Resonance Electronegativity Atomic Size Hybridization Inductive Effects

Acids and Bases

Resonance Effects
increasing quality of resonance

pKa Values 18
R CH

OH

45 CH 30

NH2

28 NH2 25

OH 10
O R C OH

O CH O C CH
O

25
O

C CH

20

C NH2

15

R C CH2 C R 9

 The Acetate Ion

O CH3 C OH
-H+
Base

Acids and Bases

O CH3 C O

acetic acid

O CH3 C O

acetate ion Resonance Stabilized Equivalent structures (charges on oxygens)

 The Phenolate Ion

O

Acids and Bases

O O O

More resonance structures, but not more stable than acetate Nonequivalent structures (note charges on carbon and oxygen)

Acids and Bases

increasing electronegativity

Electronegativity
pKa Values O RCH3 45 RNH2 35 ROH 18
R

CH4 NH3 H 2O HF

>45 34 16 3.5

R C CH3 20
O C NH2 15 O R C OH

Acids and Bases

increasing size

Electronegativity
pKa Values
O

HF HCl

3.5 7

F Cl

1.36 1.81

H 2O H 2S H2Se

16 7 4 3

C OH O

C S

SH

HBr

Br 1.95 H2Te I
R C SH

HI

10

2.16

Acids and Bases

Inductive Effects
Electron-withdrawing Groups Electron-donating Groups

H Cl

H C

H CH3

H C

F, Cl, Br, O, N

R, CH , B, Si

electronegative elements alkyl groups and elements less electronegative than carbon pull electron density push electron density toward carbon away from carbon

Acids and Bases

Inductive Effects
Chlorine helps to stabilize CO2 by withdrawing electrons

H Cl

H O C O

This effect diminishes with distanceit extends for about 3 bonds

H H H Cl C

O
H
H H

C O

Acids and Bases

increasing electronegativity

Inductive Effects
pKa Values 3.13
CH Cl COOH CH2 Cl Cl CH Cl COOH

increasing substitution

I Br Cl

CH2 COOH

4.75

CH2 COOH 2.87 CH2 COOH

COOH 2.81

2.81 2.66

1.29

CH2 COOH

Cl

C Cl

COOH

0.65

e- pair acceptor electron poor may possess formal positive charge incomplete octets greatly reduced e- density those that can yield e- poor species

Electrophiles
R R C+ R
: CH2

R.

X.
NO2+ R C+ O

X2 in r tic s lvent
O R C O OH

X+

AlCl3
H

CO2 H2O

SO3 SO3H
+

H CH3

AlCl4

BF3 FeBr3

Nucleophiles
e- pair donor excess negative charges fractional negative charges may have a lone pair e-

OHRONH 2-

CN-

R :R C R
R

O C O
-

X-

O-