Mechanistic Summary

1. Initiation: Involves homolytic cleavage of the X−X bond to generate X∙ radicals.

Initiation is endothermic, and the energy requirement is usually met by thermal
treatment or photoirradiation.

2. Propagation I: Abstraction of a H atom by the X∙radical, to produce a R−H2C∙

radical. This transformation usually takes place via a [R−H2C⋅⋅⋅H⋅⋅⋅X]‡ transition state.
Also, this process is endothermic

3. Propagation II: This stage involves the abstraction of X atom from X−X by the the
R−C∙ to produce R−H2C−X. This process occusrs via a transition state that looks so
something like this:[R−H2C∙⋅⋅⋅X⋅⋅⋅X]‡. This process, if it is sufficiently exothermic,
compensates for the previous endothermic step and the reaction proceeds.

4. Termination: Involves radical-radical recombination.

Now let us look at the energetics of the reaction. The first propagation step is exothermic for
fluorine and this explains its extreme reactivity. For the subsequent halogens, it becomes
increasingly endothermic from chlorine to iodine. This trend can be explained on the basis
of decreasing bond strengths of H−X bond. (Data given in the table above)

Now let me compare to extremes, fluorination of methane and iodination of methane. As

one can observe, the first propagation step for fluorination is not only exothermic, but it also
has a small activation barrier.

Thus in the transition state, [H3C⋅⋅⋅H⋅⋅⋅F]‡, the H−CH3 distance is only slightly greater than
that in CH4, and H−CH3 bond is weaker than the H−F bond. Thus only a slight shift of the
hydrogen atom towards the fluorine radical is sufficient to break the carbon-hydrogen bond
and form the fluorine-hydrogen bond. This kind of a transition state is called an early
transition state, and is typical of fast,exothermic processes.

In contrast, iodination displays a late transition state which is typical of slow,endothermic

processes.The activation barrier for the first propagation step is relatively high, in fact it is
almost the same as the endothermicity of the reaction. The transition state is not reached till
the the carbon-hydrogen bond is almost fully broken, and the hydrogen-iodine bond is fully
formed.
These rules about transition states are called Hammond's Postulates, and I encourage you
to read about them.

Now, indeed the reason why iodination doesn't proceed is that even though final step is
exothermic it doesn't release sufficient energy to compensate for the extremely endothermic
first step. Thus, the net reaction is endothermic.

However, it is not the exothermicity of H−X bond formation that drives the halogenation
reaction, rather it is the energy released upon −C−X bond formation (in the second
propagation step) that ensures reaction spontaneity. (this can be seen in the data presented
in the table)

This is why bromination, or for that matter chlorination can take place.