Free Radical Stability

jeechemistry.org /2015/09/free-radical-stability/
organicchemistrybyanand
The bottom line is that radicals are electron deficientand that any factor which either helps to
donate electron density to the half-filled orbital, or to spread that unpaired electron out
over a larger volume(a.k.a delocalize it) will stabilize the radical
There were a total of seven factors we discussed. You might initially find it hard to keep track of
the factors we mentioned. Thats OK, because interestingly, there is one measurement which
can help us keep all of these factors straight.
Its called Bond Dissociation Energy [BDE]. You might be familiar with it already!
What many people take some time to realize is that BDE is a measure of the energy required
for homolytic bond cleavage, and as we discussed earlier, homolytic bond cleavage leads to
the formation of free radicals [heterolytic bond cleavage, which is much more common in
organic chemistry, leads to the formation of at least one charged species [ions]]. Therefore, BDE
is essentially a measure of free radical stability.
This free radical stability connect help to understand the relation of bond dissociation energies
with free radical stabilities. .
Lets look at a quick representative example. Take two molecules methane (CH4) and water
(H2O). Which has the weaker bond to H ? Thinking back to some of the chemistry weve talked
about earlier, such as acid base reactions, it might be tempting to say that OH is weaker than
CH, since we can think of many strong bases which will deprotonate water [pKa = 15.7], but
very few that will deprotonate alkanes [pKa = 50].
However when we look at the BDEs, we see that HOH is 118 kcal/mol and H3CH is 104
kcal/mol. So the CH bond is weaker? What gives?
If youre thinking about BDEs and acid-base reactions, youre using the wrong mental model.
Acid base reactions involve heterolytic cleavage . Instead of stabily of ion we need to look at the
stability of the free radicals
Heres an example of what we need to look at in this case :-

Note how were forming a H radical in both cases. Whats different is the identity of the other
radical.
That leads us to comparing the stability of H3C and HO , and we learned previously that [all
else being equal] the stability of free radicals decreases as we go from left to right across
the periodic table, since O is more electronegative than C and that partially empty orbital is
being held more closely to the positively charged nucleus.
The bottom line for this is that bond dissociation energy is correlated to free radical
stability. Low bond dissociation energies reflect the formation of stable free radicals, and

high bond dissociation energies reflect the formation of unstable free radicals
If we keep one variable constant and vary the other variable, we can analyze the influence of
structure on free radical stability
Here were going to keep Has the variable which is the same, and by examine the trends which
influence free radical stability in a new light.
Lets look at these seven factors in turn:Stability increases in the order methyl < primary < secondary < tertiary
Free radicals are stabilized by resonance
Free radicals are stabilized by adjacent atoms with lone pairs
Free radicals increase in stability as the electronegativity of the atom decreases
Free radicals increases in stability as we go down the periodic table (larger size)
Free radicals decrease in stability as we go from sp3to sp2to sp hybridization
Adjacent electron withdrawing groups decrease the stability of free radicals.

Factor #1: Stability increases in the order methyl < primary < secondary < tertiary
Note that the BDE of C-H bonds decreases as we go from methyl to primary to secondary to
tertiary. They are easier to break since homolytic bond cleavage results in a more stable radical.

Factor #2: Free radicals are stabilized by resonance:Note the difference in bond strengths between the (primary) C-H bond of propane and of the
alkyl C-H bond of propene. The sizeable difference [~13 kcal/mol] is a reflection of the greater
stability of the resonance-stabilized allyl radical.
Although not directly comparable, look at the C-H bond strength when it is adjacent to two
alkenes [76 kcal/mol]. This doubly allylic CH bond is even weaker, reflecting the fact that a
greater number of resonance forms are available for the radical species

Factor #3: Free radicals are stabilized by adjacent atoms with lone pairs:Note the difference in bond strengths between the C-H bond of methane [104 kcal/mol] and that
of methanol [95 kcal/mol]. In between we have the C-H bond of fluoromethane [101 kcal/mol].
Note that even though fluorine is more electronegative than H, the presence of the lone pairs on
F is actually stabilizing relative to H.

Factor #4: Across the periodic table, free radical stability decreases with
increasing electronegativity:Note the difference between H-CH3 [104], H-OH [119] and H-F [136]. The most electronegative
element has the leaststable free radical and this is reflected in the higher bond strength. [psst
HNH2seems to be a bit of an outlier here.

Factor #5: Down the periodic table, free radical stability increases with increasing
size of the atom

Look how the BDE decreases as we go from H-F [136] to H-Cl [103] to H-Br [87] to H-I [71].
As we should expect by now, the iodide radical is the most stable, since the orbital is larger in
size and is therefore spread out over a larger volume. further away from the nucleus, therefore
feeling less effective nuclear charge than would a smaller atom.

Factor #6: The stability of the free radical decreases as the orbital is held closer to
the nucleus.
Look what happens to the bond strength as we go from ethane, which is sp3hybridized [98
kcal/mol] to ethene [sp2, 109 kcal/mol] to acetylene [sp, 125 kcal/mol].
This is largely the same effect as #5 above the farther away from the nucleus the half-filled
orbital is, the more stable it will be.

Factor #7: electron withdrawing groups destabilize free radicals.

To isolate this effect its important to look at examples where the electron-withdrawing group
cannot donate a lone pair to the radical (see factor #3).
One good example is comparing the C-H strength in ethane vs. trifluoroethane.