Hydrogen Abstraction by Halogen Radicals
An Illustration of the Hammond Postulate
Fluorination, Chlorination and Bromination of Methane.
Transition State Structures for H-Abstraction.


The transitions state structures for the H-abstraction from methane by fluorine, chlorine and bromine have been determined with quantum-mechanical methods and the structures can be viewed with CHIME.


 

F

Cl

Br

C-H in TS

1.153

1.438

1.600

C-H in CH4

1.085

1.085

1.085

d(C-H)

0.068

0.353

0.515

H-X in TS

1.350

1.431

1.527

H-X in HX

0.934

1.280

1.436

d(H-X)

0.416

0.151

0.091

<(H'-C-H') in TS

112.1

116.4

117.6

(<(H'-C-H'))

2.6

6.9

8.1

<(H-C-H') in TS

106.7

101.2

99.2

d(<(H-C-H'))

-2.8

-8.3

-10.3


The later the transition state, the more radical character there is in the hydrocarbon fragment. The more radical character, the more differentiation is possible between primary, secondary and tertiary carbons.

Enjoy!

Worksheet