3 Factors That Stabilize Free Radicals

by J AM ES

in ORGANI C CHEM I STRY 1

In the last post we introduced free radicals neutral,

electron-deficient chemical species with a partially filled
orbital and learned that they are highly reactive
intermediates in organic chemistry.
In this post well cover two of the most important concepts
concerning these species: theirgeometry, and
their stability.
Its this latter concept that well see is particularly
important for understanding many free-radical reactions in
organic chemistry. [Spoiler: the factors that affect free
radical stability are the same factors that stabilize
carbocations [discussed previously here]
Lets talk a bit about stability first, and then circle back to
their structure. Being electron deficient, you might already
have a hunch regarding factors that might stabilize free
radicals. Waaaay back, we talked about how a
considerable portion of organic chemistry can be
explained simply by understanding that: 1) opposite
charges attract (and like charges repel), and 2) the
stability of charges increases if it can be spread out over a
greater volume. These still apply here!
Electron poor species are stabilized by neighboring atoms
that can donate electron density. [if youre poor, it helps
to have rich neighbors]. The most common way to
interpret rich neighbors here is the observation
that increasing the number of alkyl groups on the
carbon bearing the free radical increases its
stability. Radical stability increases in the order methyl
< primary < secondary < tertiary. [For a second, more
conceptually complex example, see the bottom of the
post]. **

Secondly, we have also learned that any factor which can

lead to the electron deficient site
beingdelocalized [spread out] over a larger area will also
stabilize electron poor species. Previously, for example,
we saw that the positive charge of a carbocation was
considerably stabilized when it was adjacent to a bond.
Thats because the carbocation is sp2 hybridized and
bears an empty p orbital, allowing for overlap with the
adjacent p orbitals and therefore leading the positive
charge to be delocalized over multiple carbon atoms, in a
manner that is most easily grasped by drawing resonance
structures.
Carbocations are flat so its easy to see how the p orbital
could be in line with adjacent p orbitals of a double bond.
But what about the geometry of free radicals?

If we draw out the electrons in a typical alkyl free radical,

we see that there are three bonding pairs and a single
unpaired electron, for a total of four occupied orbitals. By
analogy to, say, amines, we might expect that the
hybridization of the molecule to be sp3 and geometry of a
free radical would be trigonal pyramidal. Thats actually a
good approximation, except that the pyramid is a little
shallower than it is for molecules which have a full lone
pair. ** [see note below]
When the free radical is adjacent to a bond, theres a
significant stabilization to be obtained if the p orbitals are
all in line so they can overlap [conjugation] with each
other. Overlap is increased (and the molecules energy
lowered) if the shallow pyramid is flattened out. Its a
good approximation to think of a free radical adjacent to a
bond as being sp2 hybridized.
So what does this all boil down to? The electron-deficient
free radical can be delocalized over multiple
carbons. Therefore, free radicals are stabilized by
resonance.
If you read the article on the stabilization of carbocations,
you might notice something: the same factors which
stabilize free radicals are also the same factors which
stabilize carbocations!
Quiz time: one of the most stable free radicals known is
the triphenylmethyl radical, discovered by Moses
Gomberg in 1900. In the absence of oxygen, this radical is
indefinitely stable at room temperature. Can you identify
the factors which might make this free radical particularly
stable?

Next Post: What Factors Destabilize Free Radicals?

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[Optional for more advanced students]
In addition to alkyl groups, free radicals are also stabilized
by adjacent groups with lone pairs, such as oxygen and
nitrogen. At first thought, oxygen might not seem like
much of an electron donating group, since its quite
electronegative. However, oxygen does have two lone
pairs of electrons. How might these be involved?
The adjacent oxygen atom can donate electron density to
the half-empty p orbital, which is a stabilizing interaction.
The orbital picture looks like this.

Yes,
theres an electron in the antibonding orbital, but on the
whole the interaction is stabilizing since bonding electrons
outnumber antibonding electrons here.