Professional Documents
Culture Documents
Mechanistic Summary
Mechanistic Summary
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.
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)
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.
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.