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Electron Delocalization (Resonance) : CH CH CL .. ..

The document discusses various structural effects on molecules, including π electron delocalization (resonance), hyperconjugation, inductive effects, and hydrogen bonding. It also covers acid-base theories, including Brønsted-Lowry and Lewis acid-base concepts. Key factors that influence acid strength are described, such as resonance, electronegativity, atomic size, hybridization, and inductive effects. Examples of electrophiles and nucleophiles are also provided.

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Karl Calilung
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61 views

Electron Delocalization (Resonance) : CH CH CL .. ..

The document discusses various structural effects on molecules, including π electron delocalization (resonance), hyperconjugation, inductive effects, and hydrogen bonding. It also covers acid-base theories, including Brønsted-Lowry and Lewis acid-base concepts. Key factors that influence acid strength are described, such as resonance, electronegativity, atomic size, hybridization, and inductive effects. Examples of electrophiles and nucleophiles are also provided.

Uploaded by

Karl Calilung
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Structural Effects

electron delocalization (Resonance)


CH2 .. CH Cl : ..
.. O C .. .. NH 2 .. NH 2

.. Cl : ..

:O: CH3 C .. O H ..

Structural Effects
electron delocalization (Resonance)

Structural Effects
electron delocalization (Resonance)

Structural Effects
electron delocalization (Resonance)

:O:

:O: C H

.. :O

N+

.. :O:

.. NH2

Hyperconjugation

Structural Effects
H H C CH CH 2 H

H H

H C CH CH2

..-

..+ H C CH CH2 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 C H ..

H
+

H H C H

..
-

Structural Effects
Hyperconjugation
H H C C H O H
H H
+

H C C

O H

Structural Effects
+

CH 3

CH 3

CH 2

CH 2 H 3C

CH3 C
+

CH 3

H :CH 3 O2N C: H H
3 -

. CH

C. H

Inductive Effect
with excess positive charges R N R R
+ +

Structural Effects

Electron attracting inductive effect


NH 3
+

NO2

those with electronegative atoms NH 2 OH OCH 3

Cl Br groups exhibiting orbital electronegativity C N N N

those with easily polarizable valence electrons I


-

Inductive Effect

Structural Effects

Electron attracting inductive effect


H3C Cl
CH3 CH2 Cl
CH3 H3C N CH3
-+

CH3

CH2

O H

Inductive Effect
alkyl groups CH3 negative groups COO
-

Structural Effects

Electron repelling inductive effect

O H3C C O
--

H3 C

H 3C CH C N H 3C

O R C O
C

O R S O O

O
O

Steric Effect

Structural Effects

Hydrogen Bonding
F O N

Structural Effects
F O N H H H

H H H

H R H O H H

H
OH OH

O H O
O R

O H H

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 + H2O Br + H3O

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 + H2O Br + H3O

HBr

Br

O H H

acid

base

conjugate base

conjugate acid

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

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 H3O+

Examples of Lewis Bases:


NH3 H2O Cl

Acids and Bases

Acids and Bases


pH = log[H3O+]
HA + H2O
A
A + H3O

Ka =

H3O
HA

pKa = log (Ka)

Acids and Bases

Acid Strength
HA + H2O H3O+ +
AE N E R G Y

A-

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

AHA
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 OH

R CH3
CH3

45

R NH2

28

30
NH2 25

OH 10

O CH3O C CH3

25
O

O R C OH
5

O R C CH3
O O

20

R 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
O
O

Acids and Bases


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

CH4

>45

RCH3 45

C CH3 20 O

NH3 H2O
HF

34 16
3.5

RNH2 35 ROH 18
R

C NH2 15

O R C OH
5

Acids and Bases


increasing size

Electronegativity
pKa Values

O
HF HCl 3.5 7
9 10

F Cl

1.36 1.81

H2O
H2S H2Se H2Te

16
7 4 3

R C OH O R C SH
S R C SH

HBr

Br 1.95 I

HI

2.16

Acids and Bases

Inductive Effects
Electron-withdrawing Groups Electron-donating Groups

Cl

CH3

F, Cl, Br, O, N

R, CH3, 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

Cl

O C O

This effect diminishes with distanceit extends for about 3 bonds

Cl C C C

O O

Acids and Bases


increasing electronegativity

Inductive Effects
pKa Values 3.13

increasing substitution

I Br Cl

CH2COOH

CH3 Cl

COOH

4.75

CH2COOH 2.87 CH2COOH 2.81

CH2
Cl

COOH 2.81
1.29

Cl
Cl

CH
Cl C Cl

COOH
COOH

F CH2COOH

2.66

0.65

e- pair acceptor
electron poor

Electrophiles
R R C+ R
: CH2

R.

may possess formal positive charge


incomplete octets greatly reduced e- density those that can yield e- poor species
+

X.
NO2+
R C+ O

X2 in protic solvent X
O R C O OH

AlCl3
AlCl4

CO2 H2O

SO3 SO3H
+

CH3

H+

BF3 FeBr3

Nucleophiles
e- pair donor

excess negative charges


fractional negative charges

OHROX-

CN-

may have a lone pair e-

R R C: R
R

O C O-

NH2N3-

O-

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