Today:

❑ Energy diagrams
❑ Nucleophiles and
electrophiles
❑ Curved-arrow presentation
of reaction mechanisms
❑ Types of electron flows
❑ Examples
 Energy Diagrams

• An energy diagram is a schematic representation of the energy changes

that take place as reactants are converted to products.
• An energy diagram indicates how readily a reaction proceeds, how many
steps are involved, and how the energies of reactants, products and
intermediates compare.

E
 6.6 Reading Energy Diagrams

Transition States Versus Intermediates

Hammond Postulate
 6.6 Reading Energy Diagrams

Kinetics Versus Thermodynamics

 Kinetics refers to the rate of a reaction.

 Thermodynamics refers to the equilibrium between reactants and products.

Thermodynamics Kinetics

Potential Potential
energy energy Ea

Reactants Reactants

Products Products

Reaction coordinate Reaction coordinate

 6.6 Reading Energy Diagrams

Potential Potential
energy energy

E+F E+F
A+B A+B
C+D C+D

Reaction coordinate Reaction coordinate

 At low temperature, the reaction that forms E and F will be more rapid, even though

this reaction does not produce the most stable products.

 At high temperature, equilibrium concentrations will be quickly achieved, favoring

formation of C and D.
Catalysts
Polar covalent bonds in organic compounds
https://socratic.org/questions/54da3f30581e2a6b292a254b
 6.7 Nucleophiles and Electrophiles

Nucleophiles

• A nucleophilic center is an electron-rich atom that is capable of donating

a pair of electrons.

Any atom that possesses a localized lone pair or negative charge can be

nucleophilic.
Typical Nucleophiles

O, N, carbanion, and p bonds are nucleophilic centers

 6.7 Nucleophiles and Electrophiles

Electrophiles

 An electrophilic center is an electron-deficient atom that is capable of

accepting a pair of electrons.
 Carbocations

 A carbocation has an empty p orbital. The empty p orbital functions as a

site that can accept a pair of electrons, rendering the compound

electrophilic.
Carbocations
 Hyperconjugation

• s-p hyperconjugation

H
Carbocation rearrangement
Stability of carbocations
p-p conjugation
 6.8 Mechanisms and Arrow Pushing

 A reaction mechanism is a detailed description of how bonds are broken

and formed as starting material is converted to product.

 The curved arrows illustrate the flow of electrons and are used to show the

mechanism of a reaction.

The tail of every curved arrow shows where the electrons are coming from.

The head of every curved arrow shows where the electrons are going.
 Bond formation

The tail must be placed on either a bond or a lone pair.

 Never place the tail of a curved arrow on a positive charge.

 Bond formation

 The head of a curved arrow must be placed so that it shows either the formation

of a bond or the formation of a lone pair.

 Bond formation

Avoid drawing an arrow that violates the octet rule. Specifically, never draw an

arrow that gives more than four orbitals to a second-row element.

 In the first example the head of the curved arrow is giving a fifth bond to the

carbon atom. This violates the octet rule.

Bond cleavage
Predict the product according to the shown curved arrow(s)

a) b)

c) d)
 Four basic patterns of arrow pushing

Nucleophilic Attack

The first pattern is nucleophilic attack, characterized by a nucleophile

attacking an electrophile.

Nucleophile Electrophile
 6.8 Mechanisms and Arrow Pushing

Two ways to draw arrow pushing:

Nucleophile Electrophile
 6.8 Mechanisms and Arrow Pushing

Loss of a Leaving Group

 6.8 Mechanisms and Arrow Pushing

Proton Transfers

The third pattern —— a proton transfer

 6.8 Mechanisms and Arrow Pushing

Rearrangements
 6.9 Combining the Patterns of Arrow Pushing

All ionic mechanisms, regardless of how complex, are just different

combinations of the four characteristic patterns.

Proton transfer Loss of a Carbocation Nucleophilic

leaving group rearrangement attack