Chapter 3

Chapter 3: Radical Halogenation
Pollution Nature
− 
O O H O
Superoxide Hydroxy
radical
Guanine
N
O
O O O
Radical Halogenation And Bond Strength
Reactions require bond breaking and bond making

Bond strengths: homolytic cleavage
∆H
A B A· + B · Radicals
∆H = DHº = Bond dissociation energy (kcal mol−1)

This process contrasts with heterolytic cleavage
+ −
A B A + B
facile
+ −
For example: H2O + H2O H3O + OH
but H OH, DHº = +119
Bond Dissociation Energy Tables
To the left of the PT: Getting weaker
Down the PT: Getting weaker
Weaker
Recall: ∆G° = ∆H° − T ∆S°

∆H° = (sum of strength of bonds broken) –
(sum of strengths of bonds made)
Example: Use Table to calculate

CH3–OH + H–I CH3–I + H–OH ∆H° = ??
CH3–OH + H–I CH3–I + H–OH
93 71 57 119
164 – 176 = –12 kcal mol−1

C-H Bond Strengths
To functionalize alkanes, we need to break C H
But: Are all C–H bonds the same ?
Secondary
 No!
Tertiary
Primary
DHº s decrease along the series:

CH4 > Rprim―H > Rsec―H > Rtert―H


Why?

Structure Of Alkyl Radicals
R is sp2-hybridized.
Remember BH3!
Substitution stabilizes the radical. How?

Hyperconjugation
p-Orbital (with single e) overlaps with
bonding molecular orbital of
neighboring C-H (or any other) bond.
Hyperconjugation stabilizes
C-H
C C E 2p bonding
MO
More Neighboring Bonds:
More Hyperconjugation
Prediction: The more substituted

C-H should be more reactive
Radical Halogenation:
Methane And Chlorine (Kcal Mol−1)
hv, ∆
CH3 H + Cl Cl CCl4
CH3 Cl + H Cl
105 58 85 103
∆Hº = −25
Exothermic, but needs heat (∆) or light (hv) to start
Mechanism Not one step, but several:

hv or ∆
1. Initiation: Cl2 2 Cl ∆Hº = +58
“lighting
the match”
How does the Cl–Cl bond break?
Thermally: Vibrational
energy gets
sufficiently large to
cause bond breaking.
Photochemically:
Absorption of
photon causes
excitation of
bonding electron to
antibonding
molecular orbital.
No stabilization:
no bond
2. Propagation (“fire”): A radical chain mechanism
a. CH4 + Cl  CH3 + HCl ∆Hº = +2 up!

105 103
b. CH3 + Cl2  CH3Cl + Cl ∆Hº = −27 down!

58 85
[a. + b.]: CH4 + Cl2  CH3Cl + HCl ∆Hº = −25

Note: Initiation step does not enter into equation. Only a
few Cl∙ needed to convert all of the starting material.
3. Termination: 2Cl  Cl2
Kills
CH3 + Cl  CH3Cl propagation
CH3 + CH3  CH3 CH3 Anim
Orbital Picture Of H·
Abstraction
Symbol for
Partial radical TS
character δ∙
Fast!
Lose Gain
105 103
Potential energy diagram of propagation steps
gives picture of the energetic “ups and downs”:
Dylan
Movie
Other Halogenations Of Methane
Compare important DH º values:
CH3 X
F2 Cl2 Br2 I2 HF HCl HBr HI F Cl Br I
38 58 46 36 136 103 87 71 110 85 70 57
Initiation OK for all First propagation step: Second propagation step:

Makes HX  Gets worse Gets worse
Reactivity: F2 > Cl2 ~ Br2 > I2 won’t go!

explodes good!
Why?
Cl2 faster than Br2
CH3―X
F2 Cl2 Br2 I2 HF HCl HBr HI F Cl Br I

38 58 46 36 136 103 87 71 110 85 70 57
CH3--H 105 kcal mol−1 Won’t go!

Endothermic
Why does reactivity (rate) follow the order F2 > Cl2 > Br2?
Rate determined in the first propagation step by
H―X. Let’s compare the position of the
transition states along reaction coordinate.
Early TS  fast , exothermic step ( F). Hammond

Postulate
Late TS  slow , endothermic step ( Br, I).
Looks like starting materials Looks like products
George S.
Hammond
(1921–2005)
Comparison Of Potential-Energy Diagrams Of The Reaction
Of CH4 With F2, Cl2, Br2, And I2, Respectively
Selectivity For Different C-H Bonds
CH3
CH2
CH3 CH3 CH3 C CH3 prim, sec, tert
H
Cl2, hv
CH3CH2CH3 CH3CH2CH2Cl + CH3CHCH3
−HCl
Cl
Statistical (expected) 3 : 1
R―H (expected) Less (prim) More (sec)
Found (25 ºC) : 43 : 57
Reactivity per H: 43/6 = 7.2 57/2 = 28.5
1 : 4
Secondary C-H is more reactive than primary C-H
Transition states radical-like;
reflect relative stabilities of radical
products
Compare: CH4 + Cl Ea = 4 kcal mol−1
Because the TSs resemble the ensuing radicals,

the TS leading to the sec radical is lower in
energy than that leading to the primary radical
What about tertiary C-H?
CH3 CH3 CH3
Cl2, hv
CH3 C H
-HCl
ClCH2 C H + CH3 C Cl
CH3 CH3 CH3
Statistical (expected) 9 : 1
R―H (expected) Less (prim) More (tert)
Found (25 ºC) 64 : 36
Normalized per H: 64/9 = 7 36/1 = 36
1 : 5
Result: Relative reactivity (selectivity) in
chlorinations at 25ºC: Tert : Sec : Prim = ~ 5 : 4 : 1
Selectivity And Other Halogens
CH3
(CH3)3CH + F2  FCH2CH + (CH3)3CF 9:1
CH statistical !
3
(CH3)3CH + Br2  (CH3)3CBr only !

Just to get a feel for the numbers……..
Selectivities vary extensively with the

reagent employed, e.g., ICl, ROCl, R2NBr,
with temperature, and solvent.

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Chapter 3: Radical Halogenation

Reactions require bond breaking and bond making

∆H = DHº = Bond dissociation energy (kcal mol−1)

Down the PT: Getting weaker

Recall: ∆G° = ∆H° − T ∆S°

Example: Use Table to calculate

164 – 176 = –12 kcal mol−1

DHº s decrease along the series:

Substitution stabilizes the radical. How?

Prediction: The more substituted

Mechanism Not one step, but several:

a. CH4 + Cl  CH3 + HCl ∆Hº = +2 up!

b. CH3 + Cl2  CH3Cl + Cl ∆Hº = −27 down!

[a. + b.]: CH4 + Cl2  CH3Cl + HCl ∆Hº = −25

Initiation OK for all First propagation step: Second propagation step:

Reactivity: F2 > Cl2 ~ Br2 > I2 won’t go!

F2 Cl2 Br2 I2 HF HCl HBr HI F Cl Br I

CH3--H 105 kcal mol−1 Won’t go!

Early TS  fast , exothermic step ( F). Hammond

Looks like starting materials Looks like products

Compare: CH4 + Cl Ea = 4 kcal mol−1

Because the TSs resemble the ensuing radicals,

(CH3)3CH + Br2  (CH3)3CBr only !

Selectivities vary extensively with the

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