The hybridisation and therefore shape of a radical can be anywhere
between sp3 and sp2, although the latter
is the more common (with the unpaired electron in the p orbital)
- there is some preference for it, shown by the difficulty of
forming radicals in bridged species that cannot reach sp2
hybridisation.
Radicals are not particularly stable in general, as noted before,
so their stability is only a relative term used to compare radicals
with radicals. They can be stabilised by;
Steric Relief: If the radical
to be formed is planar, then for centres with bulky substituents
there will be steric relief obtained in forming the radical
- as with carbocations (see the nucleophilic
substitution section on these), though to a lesser extent.
Conjugation/Resonance: Again,
as with both carbocations and carbanions, a radical that can
delocalise across π systems will
be stabilised. It should be remembered that resonance may allow
the radical to react at a different centre to the one at which
it was formed.
Steric Protection: This
is not technically stability in thermodynamic terms, but more
in kinetic terms - if there are sterically bulky groups around
the radical centre, it will be difficult for anything to reach
the radical and react with it - conveying an apparent stability.
In fact, these radicals are quite likely to be the ones trapped
and observed, because their steric protection prevents them
from reacting at all.
Weakness of the original bond:
For example whilst oxygen is not particularly stable in
a radical state, relative to the rather weak O-O bond oxygen
radicals are not disfavoured - similarly for other weak bonds
mentioned on the previous page.
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