CHEM 203

Topics Discussed on Sept. 8

The oxidation state of atoms possessing a formal charge: the case of NH4+:

• the formal charge on N is + 1

H • N is more electronegative than H (3.0 vs. 2.1)
• Formally, N has "stolen" 1 electron from each of the 4 H's
N H
H • Formally, N has aquired 4 electrons in this bonded state
H
The oxidation state of N in NH4+ is: – 4 (bond polarization) + 1 (formal charge) = – 3
The electronic configuration of N in this molecule resembles that of neon

Issues of electrostatic imbalance (formal charges, oxidation states, bond polarization, molecular
polarity, etc.) as significant aspects of the chemistry of organic molecules containing
heteroatoms that possess unshared (lone, nonbonding) pairs of electrons, such as N, O, S, P,
halogens, etc.:

H
CH3 N CH3 OH CH3 O CH3 CH3 SH CH3 S CH3 CH3 P CH3
H CH3

Ability of heteroatoms possessing unshared pairs to establish bonds by donating an electron pair
to an appropriate species capable of accepting that electron pair

Principle: an atom / molecule can function as an acceptor of electron pairs only if it possesses a
vacant orbital that can accommodate an incoming electron pair.

Example of a molecule that can function as an acceptor of electron pairs: BH3 (borane)
vacant, atomic the B atom has an incomplete
p-type orbital H octet: it can accept 2 additional
on the B atom H B electrons in a vacant, p-type
H atomic orbital to acquire a noble
gas-like electronic configuration

Predictable (and experimentally verifiable) reaction between, e.g., dimethyl sulfide and BH3:
vacant p-type orbital
H H H
H B B Important: notice
H mix CH3 H the formal charges
CH3
S S on S and B
unshared CH3
CH3 electron pairs

Lewis base: a species possessing one (or more) unshared electron pair that could possibly be
employed to establish a new bond by donation to a suitable acceptor
CH3-S-CH3 is a Lewis base because the S atom has 2 unshared pairs of electrons
 Lecture of Sept 8 p. 2

Lewis acid: a species possessing a vacant orbital that could possibly be employed to establish a
new bond by acceptance of an electron pair from a suitable donor
BH3 is a Lewis acid because the B atom has a vacant orbital

Dative bonds: those formed through the donation of an unshared pair of electrons from a Lewis
base into a vacant orbital of a Lewis acid

Principle: one may find that a Lewis acid accepts electron pairs only from particular Lewis bases.
Likewise, a Lewis base may be inclined to donate electron pairs only to particular Lewis acids

Necessity to distinguish between Lewis acidity / basicity (intrinsic molecular properties

determined by the electronic configuration of atoms within molecules) and the actual expression
of such potential reactivities in the course of a reaction

Nucleophile: a Lewis basic agent (= one that possesses an unshared pair of electrons) that
actually expresses such Lewis basicity during a chemical reaction

Lewis basic CH3-S-CH3 functions as a nucleophile in the above reaction

Electrophile: a Lewis acidic agent (= one that possesses a vacant orbital) that actually expresses
such Lewis acidity during a chemical reaction

Lewis acidic BH3 functions as an electrophile in the above reaction

Equivalently, one can distinguish between:

Lewis acidic / Lewis basic character: a property determined solely by the
electronic configuration of a molecule
and

electrophilic / nucleophilic character: ability of a Lewis acid / base to express

their inherent reactivity

Curved arrows formalism to represent the movement of electrons (not of atoms) during a
chemical reaction; i.e. the mechanism of the reaction
example: the red arrow below depicts the mechanism of the reaction of CH3SCH3 with BH3:

H
H B H H
CH3 H B borane-dimethyl sulfide
CH3 H
S S complex: a commercial
CH3 form of borane
CH3

Interactions between a Lewis acid and Lewis base as a fundamental phenomenon that governs
organic chemical reactions

Obvious case of organic reactions involving Lewis acid-base interactions: the above reaction of
borane, BH3, with dimethyl sulfide, CH3–S–CH3
 Lecture of Sept 8 p. 3

Less obvious case of organic reactions involving Lewis acid-base interactions: the SN2 reaction

Example:
large lobe of
the σ*C-I orbital
H
H–O C I H–O–CH3 + I
H
H small lobe of
the σ*C–I orbital

The CH3I in the above reaction accepts a pair of electrons into the vacant σ*C-I orbital, thereby
behaving as a Lewis acid

Reminder: bonding and antibonding orbitals always arise in pairs upon linear
combination of atomic orbitals (LCAO) leading to molecular orbitals

Bond order (BO): BO = (# electrons in bonding orbitals – # electrons in antibonding orbitals) / 2

Weakening / breaking of a generic bond A–B upon introduction of electronic density into the
corresponding antibonding orbital
–
Example: In the above SN2 reaction, the nucleophile (HO ) introduces a pair of
electrons into the vacant s*C-I orbital. As a result, the BO of the C–I bond
becomes:
– –
BO = (2 e in bonding orbital – 2 e in antiboding orbital) / 2 = 0
–
The bond between C and I vanishes and the I becomes free to "float away."

Special case of Lewis acid-base reactions: proton transfer (= protonation) reactions, i.e. Bronsted
acid-base reactions. Example:

H H
small lobe
H Cl
H N of σ*H–Cl
H N H
Cl
H H
large lobe of σ*H–Cl

Bronsted acids, Bronsted bases: proton donors (HCl above) / acceptors (NH3), respectively

Bronsted acid-base equilibria as fundamental aspects of a great many organic chemical

transformations

Electronic analogy between proton transfer reactions and SN2 reactions

Principle: the chemical behavior of a system in which proton transfers are likely to occur may be
predicted on the basis of changes in the acidity / basicity of the medium, which in turn can be
gauged from the pKa's of the reacting species. Therefore, pKa's and ΔpKa's are crucially
important to understand proton exchange equilibria
 Lecture of Sept 8 p. 4

Reminder: the pKa of a generic Bronsted acid H–A is defined as:

pKa = – log Ka, where:

[A–] [H+]
Ka = for the equilibrium: H–A H+ + A–
[AH]

consequently: acid strength and pKa's are inversely proportional, that is:
strong acids have small pKa's
weak acids have large pKa's
moreover: the dissociation of a strong Bronsted acid releases a weak Bronsted base
the dissociation of a weak Bronsted acid releases a strong Bronsted base
The following expression holds true for the acid-base equilibrium between generic Bronsted
–
acid AH and Bronsted base B :

[A–] [BH]
A H + B A + B H Keq =
[AH] [B–]

If one expresses Keq as a function of the Ka's of HA and HB, one finds that:

[A–] [H+] [A–] KaAH [B–] [H+] [BH] [H+]

KaAH = so: = and KaBH = so: =
[AH] [AH] [H+] [BH] [B–] KaBH

[A–] [BH] [A–] [BH] KaAH [H+] KaAH

Keq = = = =
[AH] [B–] [AH] [B–] [H+] KaBH KaBH

Therefore, pKeq = pKaAH – pKaBH and log Keq = pKaBH – pKaBH

Using pKa's to estimate equilibrium constants and ΔG's for Bronsted acid-base interactions:
example: we wish to predict whether the above reaction of ammonia, NH3, with hydrogen
chloride, HCl is favorable or unfavorable, and how favorable / unfavorable it is, knowing that:
+ +
pKa of NH4 ≈ + 9 (NH4 is the weaker Bronsted acid, NH3 is the stronger Bronsted base)
–
pKa of HCl ≈ – 7 (HCl is the stronger Bronsted acid, Cl is the weaker Bronsted base)

One can tell immediately that the reaction in question will be favorable, because it consumes a
+
stronger acid (HCl) and a stronger base (NH3) to produce a weaker acid (NH4 ) and a weaker
–
base (Cl ). Regardless, the equilibrium constant for the above reaction is:

[NH4+] [Cl–] [NH4+] [Cl–]

Keq = = •
[NH3] [HCl] [NH3] [HCl]
+
If one expresses the above Keq as a function of the Ka's of NH4 and of HCl:
Lecture of Sept 8 p. 5

[H+] [NH3]
NH4+ H+ + NH3 ••• Ka NH + = = 10–9 (because pKa = 9), so
4
[NH4 +]

[NH4+] [H+]
=
[NH3] 10–9

[H+] [Cl–]
HCl H+ + Cl– • = 107 (because pKa = –7), so
• • Ka HCl =
[HCl]

[Cl–] 107
=
[HCl] [H+]

[H+] 107
Keq = • = 1016
–9 +
10 [H ]

Such a large, positive Keq indicates that the reaction is highly favorable and that the
equilibrium will be strongly shifted to the right.

Additional example : the protonation of diethyl ether with acetic acid:

O O
C H C
CH3–CH2 O H O CH3 CH3–CH2 O O CH3
CH3–CH2 CH3–CH2
pKa ≈ 5 pKa ≈ –3

One can tell immediately that the reaction in question will be unfavorable, because it
consumes a weaker acid (acetic acid) and a weaker base (ether) to produce a stronger acid
(protonated ether) and a stronger base (acetate ion).
Regardless, the equilibrium constant for the above reaction may be estimated as:

[ (CH3-CH2)2OH ] [ OOC-CH3]
ΔpKa ≈ pKeq = 5 – (–3) = + 8 Keq ≈ 10–8 =
[ (CH3-CH2)2O ] [HOOC-CH3]

The reaction is clearly unfavorable, because Keq < 1

One may even estimate the equilibrium concentration of the protonated form of ether
by reasoning that:
+
• each molecule of (CH3-CH2)2OH that forms during this reaction must be accompanied
– +
by a molecule of OOC-CH3; i.e., the equilibrium concentrations of (CH3-CH2)2OH and
–
OOC-CH3 must be numerically identical.
• because Keq is so small, only an insignificant portion of the reactants will have advanced
to products at equilibrium. Therefore, the equilibrium concentrations of (CH3-CH2)2O and
HOOC-CH3 are nearly identical to the initial concentrations.
• Suppose then that the above equilibrium takes place in a solution that is initially 1M in
Lecture of Sept 8 p. 6

both ether and acetic acid. We conclude that:

numerically equal

[ (CH3-CH2)2OH ] [ OOC-CH3] 2
Keq = = [ (CH3-CH2)2OH ] ≈ 10–8
[ (CH3-CH2)2O ] [HOOC-CH3]

both nearly 1 M at equilibrium

so: [ (CH3-CH2)2OH ] ≈ Keq = 10–8 = 10–4

about one part in 10,000 of diethyl ether will exist in protonated form at equilibrium

note: the above is not a precise treatment of the equilibrium (we are ignoring solvent
effects and other important factors), but it provides a useful semiquantitative estimate
of the position of the equilibrium.