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Free Radical Reactions

by J AM ES

in ALKANES, ORGANI C CHEMI STRY 1

With rare exceptions, until now every reaction weve


discussed (acid-base, substitution, elimination, addition)
has involved the formation of bonds between an electron
pair donor (Lewis base) and an electron pair acceptor
(Lewis acid) or the breakage of bonds to generate the
same [this is called heterolytic cleavage, by the way,
since one bonding partner gets two electrons and the
other gets zero].

In this series of posts well take a detour into a corner of


organic chemistry where bonds are formed by the
combination of single electrons and bonds break through
homolytic cleavage [that is, each bonding partner
receives an equal number of electrons]. As well see,
these reactions are generally referred to as free radicals.

It all starts with a simple observation. Take an ordinary


hydrocarbon gas methane, for example, although any
alkane hydrocarbon will be suitable here. When we
combine this hydrocarbon with chlorine gas, in the dark,
nothing happens.

Heres the interesting part. Flick a switch or remove the


cover such that visible light can enter the flask, and
suddenly our methane is consumed such that carbon-
hydrogen bonds are replaced with carbon-chlorine bonds.
The final product depends on the number of equivalents of
chlorine gas lets use Cl2 in very small quantities to start
with, to keep things simple.

Whats going on here? Note that hv means light. [We


can also do this reaction with heat alone, although it
requires higher temperatures].

Before trying to understand why this happened, lets make


sure were clear on what has happened.
Lets look at what bonds have formed and what bonds
have broken. Notice that were breakingCl-Cl, C-H,
and forming C-Cl.
What reactions have we seen so far that would be capable
of such a transformation? Well, weve seen that all acid-
base reactions involve the cleavage of a bond between H
and some atom. So maybe, you might say, its possible
that somehow a hydrogen is being pulled off the carbon by
a strong base, and then the carbon attacks chlorine. But
does that make sense here?
Note that methane [CH4] would have to be the acid, and
chloride ion [Cl- ] would have to be the base. As weve
seen before, this makes NO sense as an acid base
reaction, because wed be going from a very weak acid
[CH4] to a very strong acid [HCl] and likewise a weak base
[Cl] to a strong base. This is like trying to get Niagara Falls
to flow in reverse. Not gonna happen!

Furthermore, a second piece of evidence should give


pause. If the reaction proceeded through some kind of
charged intermediate like Cl- or CH3- , we would expect
that the reaction would proceed more quickly in polar
solvents [that can stabilize charge] as opposed to
nonpolar solvents [which do not stabilize charge]. Instead,
we find that the rate of the reaction is almost completely
independent of solvent polarity. It proceeds just about as
quickly in [nonpolar] carbon tetrachloride as it does in a
polar solvent such as methanol.

So what does this mean? It is consistent with the reaction


proceeding through neutralintermediates rather
than polar ones.
Alright so how, then, might we get a neutral
intermediate?

Lets think first about that chlorine-chlorine bond, which is


relatively weak. Imagine that by heating it up or by shining
light on it [recall that light is a form of energy!] it might
break somehow. How might it break?

Option #1 would look something like this heterolytic


cleavage, where one atom receives both electrons from
the bond, while the other does

However if this was the case, then we should expect to


see a faster reaction in polar solvents, which is not the
case.
So what else might happen here?

Recall that many of the molecules weve been discussing


have a dipole. That is, two atoms sharing a bond have
unequal electronegativities, and thus unequal electron
densities one is electron rich and one is electron poor.

However here we have two chlorine atoms. They have


equal electronegativity. So we would not expect that one
chlorine should win the tug of war of electrons over the
other.

So we are left with this: What if the chlorine chlorine


bond breaks such as to give each chlorine a single
electron?
Weird, when you first see it. One note when using the
arrow pushing notation, we modify it somewhat, such that
we have single fishhooks showing where the electrons
go. Note that we can use these to show a single electron
going to each of the two chlorines.
But lets look at this a bit more closely.

What would be the charge of the chlorine atom? It has


seven valence electrons.

This species is neutral, which is consistent with the


solvent data.
Would we expect such a species to be stable? If we think
back to the octet rule, we see that each chlorine atom
bears less than a full octet of electrons. In other words,
it is electron-deficient.
We would expect such a species to be highly
reactive, since there will be a strong driving force to
form the full octet.
The whole point of this article is to say that yes, such
species do exist, and they are called free radicals [the
etymology of this term is interesting, but a little old-
fashioned and not crucial for us right now]
There are additional pieces of evidence collected over the
past hundred-odd years to support the existence of free
radicals. They arent crucial to understand, but if youre
curious you could try reading about EPR, CIDNP,
or Moses Gomberg, the father of free radical chemistry.

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