Chapter 03
Synchronous Topics
Nucleophiles & Electrophiles
Arrow-pushing notation
Acids & Bases
pH & pKa: thermodynamics
Predicting acidity
Curved Arrow Notation:
Show where the electrons “go” during the reaction.
1. Move only electrons, not charges or atoms (tail at source, point at destination)
2. Lone pairs may only form a new sigma or pi bond to the atom they started with
3. Bonding electrons may
• form a lone pair on one of the original atoms sharing the electrons in the bond
• form a new bond from one of the atoms it was originally sharing with
Poll Question
Which of these is a valid curved arrow notation?
B CH2 CH2 CH2 CH2
CH CH
H2C CH CH
H2C
H2C H2C
C
CH2 CH3
D H2C
CH
H2C
C
Respond at pollev.com/sjconnel or in the PollEverywhere app
Curved Arrow Notation & Resonance
Nitromethane:
O
N
O
Methoxymethyl cation
CH2
O
H 3C
When to look for resonance structures:
Resonance Hints: • pi bond between atoms with different EN
• lone pair on atom adjacent to electron-deficient group
• pi bond adjacent to pi bond
• lone pair adjacent to pi bond
General considerations for importance of resonance structures:
• complete octet
• negative (formal) charges on most electronegative atoms
• delocalizing charge is better than separating charges
Two types of reactions: association & displacement
Electrophile
Nucleophile
Leaving Group
Poll Question
Which species is the nucleophile?
CH3 CH3 H
H
H3C C H3C C O
O
A A CH3 H CH3
H
B C
D (none)
Respond at pollev.com/sjconnel or in the PollEverywhere app
Practice
Draw the curved arrows for this reaction. Identify the
nucleophile, the electrophile, and the leaving group.
+ H
O
Br
Brønsted-Lowry Acids & Bases
Hydrogen atom donor vs. acceptor
Conjugate acids & bases
Brønsted-Lowry Acids & Bases
O S
Guess the products of this reaction.
Draw the arrows to represent that transformation.
Identify:
acid conjugate base
base electrophile
conjugate acid nucleophile
Which species is the conjugate base?
B D
A SH + NaOCH3
S Na+
+ CH
3OH
A C
B
Respond at pollev.com/sjconnel or in the PollEverywhere app
Chemical Equilibrium: 3 cases
A A B B B B B
A A
A
A A B Keq >> 1
A B
B B A
B
A A
A A A B
A A B B B
A A A BA B
A A A A A A
A A BA B Keq ~ 1
A A A A
A A
A A A A B B
A
A A A A
A A A A A A A A
A A A B Keq << 1
A A A A
A A A A
A A A A A A
Relating Keq to thermodynamic stability
What fraction of the butane molecules are in the anti conformation vs. a
gauche conformation if the free energy difference is 3.7 kJ/mol?
Acid Strength: quantified by pKa value
𝑨𝑨− [𝑯𝑯+ ]
HA + H2O A– + H3O+ 𝑲𝑲𝒂𝒂 =
𝑯𝑯𝑯𝑯
−𝒍𝒍𝒍𝒍𝒍𝒍 (𝑲𝑲𝒂𝒂 ) = 𝐩𝐩𝑲𝑲𝒂𝒂
Base Strength
related to pKa of conjugate acid, characterized by Kb
Calculate Keq for HCN + NMeH2 pKa (NMeH3+) = 10.6
pKa (HCN) = 9.4
What species are present in the solution?
Structure of organic molecules to predict acidity
1. Charge Effect
NH4+ much more acidic than NH3
• Separating + charge from neutral species easier than + / – charges.
Organometallic complexes: Higher oxidation state = more acidic hydride
LOUDON – Chapter 3.6B
Structure of organic molecules to predict acidity
2. Element (Atom) Effect
• Which element is the acidic proton attached to?
• Acidity increases down a group (HI more acidic than HF)
• Acidity increases across the periodic table (HF more acidic than CH4)
LOUDON – Chapter 3.6A
Structure of organic molecules to predict acidity
3. Hybridization Effect
• Increasing “s” character increases the acidity of the species
LOUDON – Chapter 3.6C
Structure of organic molecules to predict acidity
4. Resonance Effect
• Consider stability of the conjugate base: delocalize the electrons?
LOUDON – Chapter 3.6C
Structure of organic molecules to predict acidity
5. Polar Effect
• Electronegative groups in the molecule can reduce electron density in
the bond between what will become the conjugate base and the proton
O
Cl O O O
OH
Cl
OH OH OH
Cl
LOUDON – Chapter 3.6C
Which species do you expect is most basic?
O
A O
B
H
N
O
C H 3N
O
D (none)
Respond at pollev.com/sjconnel or in the PollEverywhere app
