1.

Structure, Reactivity, and Mechanism

Table of Contents
1.1 Atomic Orbitals
1.2 Hybridization
1 3 Bonding in Carbon Compo
1.3 Compounds
nds
1.3.1 Carbon-Carbon Single Bonds
1.3.2 Carbon-Carbon Double Bonds
133C
1.3.3 Carbon-Carbon
b C b T Triple
i l BBonds
d
1.3.4 Carbon-Oxygen and Carbon-Nitrogen Bonds
1.3.5 Conjugation
1 3 6 Benzene and Aromaticity
1.3.6
1.3.7 Conditions Necessary for Delocalization
1.4 The Breaking and Forming of Bonds
1 5 Factors Influencing Electron
1.5 Electron-Availability
Availability
1.5.1 Inductive and Field Effects
1.5.2 Mesomeric Effect (Resonace Effect)
1 5 3 Ti
1.5.3 Time-Variable
V i bl Eff
Effects
t
1.5.4 Hyperconjugation
1.6 Steric Effects
17R
1.7 Reagentt TTypes
1.8 Reaction Types
1. Structure, Reactivity, and Mechanism
1.1 Atomic Orbitals

s orbital

p orbital
1. Structure, Reactivity, and Mechanism
1.2 Hybridization
Two Basic models developed to describe the chemical bonding
Valence Bond Theory (VBT)
the concept of mixing atomic orbitals into new hybrid orbitals
(with different energies, shapes, etc., than the actual orbitals
h b idi i ) suitable
hybridising) it bl ffor th
the pairing
i i off electrons
l t tto fform chemical
h i lb bonds
d

Molecular Orbital Theory (MOT)

LCAO-MO

Combining VBT with MOT

VBT : Utilized to explain σ-bonds

MOT : Used to explain
p π-bonds
1. Structure, Reactivity, and Mechanism
1.2 Hybridization
Valence Bond Theory (VBT)
the concept of mixing atomic orbitals into new hybrid orbitals
(with different energies, shapes, etc., than the actual orbitals
hybridising) suitable for the pairing of electrons to form chemical bonds

1. Tetrahedral structure
1 structure.
2. All C-H bonds are identical.
3. Bond angle: 109.5o

Can we explain these results

Based on atomic orbitals?
1. Structure, Reactivity, and Mechanism
1.2 Hybridization
sp3 Hybridization Tetrahedral structure,
Bond angle: 109.5o
1. Structure, Reactivity, and Mechanism
1.2 Hybridization
H H Trigonal planar structure,
sp2 Hybridization C C
H H Bond angle: 120o
1. Structure, Reactivity, and Mechanism
1.2 Hybridization
linear structure,
sp hybridization
O C O Bond angle: 180o
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds

Molecular Orbital Theory

antibonding
σ*

Symmetry (shape)
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.1 Carbon-Carbon single bonds

d ((C-C)) = 1.54 Ǻ
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.1 Carbon-Carbon single bonds

Conformation
a form of stereoisomerism in which the isomers can be
i t
interconverted
t d exclusively
l i l b by rotations
t ti about
b t fformally
ll single
i l
bonds without the breaking of any bonds

d (H-H) = 2.3 Ǻ d (H-H) = 3.1 Ǻ

Energy difference at 25 oC is 3.0 kcal.

1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.2 Carbon-Carbon double bonds

σ bond π bond

d (C-C) = 1.33 Ǻ

Free rotation along the double bond?

No conformational isomer exists in alkenes!!
Stereoisomerism exists in alkenes!!
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.3 Carbon-Carbon triple bonds

d (C-C) = 1.20 Ǻ

σ bond π bond
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds

3 3

Hybridization of Carbon sp3 sp2 sp

C-C bond length (Ǻ) 1.54 1.33 120

C-C bond strength

g ((kcal)) 83 143 194

Bond angle 109.5 120 180

% s character
h t 25 33 50
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.4 Carbon-Oxygen and Carbon Nitrogen Bonds
1. Lone pair electrons exist!!
2. Hybridization at O and N atoms is the same as C atom.
3. Draw lone pair orbitals with the appropriate geometry.
Oxygen Electron configuration: 1s22s22p4

sp3 hybrid d (C-O) = 1.42 Ǻ d (C-C) = 1.54 Ǻ

BDE = 86 kcal/mol BDE = 83 kcal/mol

sp2 hybrid
d (C-O) = 1.22 Ǻ d (C-C) = 1.33 Ǻ
120 o
BDE = 179 kcal/mol BDE = 143 kcal/mol
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.4 Carbon-Oxygen and Carbon Nitrogen Bonds

Nitrogen Electron configuration: 1s22s22p3

Hybridization
sp3 sp2 sp
of nitrogen
d (C-N) 1.47 Ǻ 1.35 Ǻ 1.16 Ǻ

BDE 73 kcal/mol 147 kcal/mol 213 kcal/mol

1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.5 Conjugation
Conjugated diene: Alternating multiple and single bonds

Partial double bond character

d (C=C) = 1.34 Ǻ

d (C-C) = 1
1.47
47 Ǻ

Normal d (C-C) = 1.54 Ǻ

Restrict rotation about the C2-C3 bond

Isolated diene: multiple bond is connected via sp3 hybridized carbon

1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.5 Conjugation
Conjugated dienes are more stable than lsolated dienes.
Evidences:
1. Heat of combustion
2. Heat of hydrogenation
3 Isomerization from isolated dienes to the corresponding
3.
conjugated dienes

Conjugation is not limited to C-C multiple bonds.

isolated enone conjugated enone

More stable
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.5 Conjugation
Conjugated dienes are more stable than lsolated dienes (4 kcal/mol).

MOT of 1,4-pentadiene vs 1,3-pentadiene.

H2C CH3

(Ethene X 2) Total energy is lower!!

The electrons are delocalized in the
whole of the conjugated system
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.5 Conjugation

Delocalization reduces the energy gap between ground and excited

states of conjugated molecules.

∆E1 ∆E2

Particle in a box

n2h2
En 
8ml 2
∆E1 > ∆E2
1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.6 Benzene and aromaticity
Benzene is remarkably stable than its hypothetical cyclohexa-1,3,5-triene!!
+ H2 H1 = -28.6 kcal/mol

+ 3 H2

hypothetical
cyclohexatriene ∆E = resonance energy

H4 = -49.8
-49 8 kcal/mol

4 H2 H2

H = -98 kcal/mol H = -23 kcal/mol

1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.6 Benzene and aromaticity
MOT of benzene

d (C=C) = 1.33 Ǻ
d (C-C) = 1.54 Ǻ
d (C-C) = 1.40 Ǻ
All C-C bonds are identical!!

A set of filled MOs is associated with exceptional stability of benzene.

1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.6 Benzene and aromaticity

Aromaticity
Requirements for aromaticity
1. Cyclic
2 Planar
2.
3. Number of π-electrons = 4n + 2 (Huckel’s rule)

More Examples of Aromatic Compounds

1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.6 Benzene and aromaticity
Why aromatic compounds follow Huckel’s rule?

6 π-electrons 4 π-electrons

A set of filled MOs is associated with exceptional stability of aromatic compounds!!

1. Structure, Reactivity, and Mechanism
1.3 Bonding in Carbon Compds
1.3.7 Conditions necessary for delocalization

The two C-O

C O bond are identical!!

The limitation could be overcome using resonance structure

1. The structures must contain the same number of paired electrons.

2. No bond breaking
3
3. Use a double-headed
double headed arrow to represent resonance structures
4. The more resonance structures, the more delocalization of π-electrons,
and the more stable the compound is
1. Structure, Reactivity, and Mechanism
1.4 Breaking and Forming Bonds
Breaking of Bonds

R + X Homolyptic fission

R X R + X
Heterolyptic
yp fission
R + X

Radical intermediates vs Ionic intermediates

Carbocation vs Carbanion

Formation of Covalent Bonds: reversal of bond breaking process

1. Structure, Reactivity, and Mechanism
1.5 Electron Availability
Two major factors to control reactivity:
1) Electronic effect
2)) Steric bulk
1.5.1 Inductive and Field Effects
Inductive Effect:
Transmission of charge through a σ bond by successive polarization

Inductive effect quickly dies

away in a saturate chain!!
Field Effect:
Transmission of charge through space electrostatic interaction

Display similar substituent effect!!

It is not easy to distinguish field effect from inductive effect.

Inductive effect is assumed to include field effect!!
1. Structure, Reactivity, and Mechanism
1.5 Electron Availability
1.5.2 Resonance Effect (Mesomeric Effect):
Redistribution of electron via π orbitals

C O C O C O

O O O
H3C H3C H3C
O O O

Resonance effect Inductive effect

B d type
Bond π orbitals
bit l (π
( bonds)
b d ) σ bond
b d
Transmission Entire conjugation system Die away quickly
range
1. Structure, Reactivity, and Mechanism
1.5 Electron Availability
1.5.3 Time-variable effects
Polarizability:
The relative tendency of a charge distribution to be distorted from its normal shape
By an external change.

Polarizability is proportional to the relative amount of electrons in molecules or ions.

1. Structure, Reactivity, and Mechanism
1.5 Electron Availability
1.5.4 Hyperconjugation:
Interaction between σ bond and π system

1. Stability of double bonds

2. Stability of carbocations

H
1. Structure, Reactivity, and Mechanism
1.5 Electron Availability
1.5.4 Hyperconjugation:
Interaction between σ bond and π system
Sometimes, hyperconjugation has reversed order of inductive effect!!
Relative magnitude of inductive effect of alkyl groups

Relative stability of alkenes bearing alkyl groups

H H H H
Me H Me H Me H H H
Me C < H C < H C < H C
Me H Me H H H H H
1. Structure, Reactivity, and Mechanism
1.6 Steric Effects
Two major factors to control reactivity:
1) Electronic effect
2)) Steric bulk

M
Me Me
Me N N Ph Me
N N N
Me Me N
M
Me M
Me

d (C-C) = 1.66 Ǻ
1. Structure, Reactivity, and Mechanism
1.6 Steric Effects
Steric hindrance

St i acceleration
Steric l ti
1. Structure, Reactivity, and Mechanism
1.7 Reagent Types

Electrophiles
- Reagents attracted to electrons participating in a chemical reaction
via
i accepting
ti electron
l t pairs
i (L(Lewis
i acids)
id )

Ex) H+, H3O+, NO2+, NO+, PhN2+, R3C+

SO3, CO2, BF3, AlCl3, Br2, ICl,
ICl O3, etc…
etc

Nucleophiles
- Reagents that tend to attack the substrate at a position of low
electron densityy ((Lewis bases))

Ex) H-, BH4-, HSO3-, HO-, RO-, RS-, CN-,

RCO2-, RCC-, RMgBr, RLi, etc…
1. Structure, Reactivity, and Mechanism
1.8 Reaction Types
General Types of Organic Reactions
1. Displacement Reaction (Substitution Reaction)
2. Addition
dd o Reaction
eac o
3. Elimination Reaction
4. Rearrangement Reaction

1. Displacement Reaction
- A type of reaction where part of one reactant is replaced by another reactant

Me N N Ph Me
N H N N
Me Me N
1. Structure, Reactivity, and Mechanism
1.8 Reaction Types
2. Addition Reaction
- A type of reaction where an atom or group of atoms is added to a molecule

H Br Br

3. Elimination Reaction
yp of reaction where a molecule loses atoms or g
- A type groups
p of atoms,, usually
y
from adjacent atoms
1. Structure, Reactivity, and Mechanism
1.8 Reaction Types

4. Rearrangement Reaction
-A type of reaction where the carbon skeleton of a molecule is rearranged to
give
i a structural
t t l iisomer off th
the original
i i l molecule
l l

-Rearrangement proceeds via intermediates that are cations

(
(most
t common),
) anions,
i and
d radicals.
di l