The Effect of Hybridization

The protons of ethyne are more acidic than those of ethene, which in turn are mo
re acidic
than those of ethane
We can explain this order of acidities on the basis of the hybridization state o
f carbon in each
compound. Electrons of 2s orbitals have lower energy than those of 2p orbitals b
ecause electrons
in 2s orbitals tend, on the average, to be much closer to the nucleus than elect
rons in
2p orbitals. (Consider the shapes of the orbitals 2s orbitals are spherical and
centered on the
nucleus; 2p orbitals have lobes on either side of the nucleus and are extended i
nto space.)
With hybrid orbitals, having more s character means that the electrons of the
anion will, on the average, be lower in energy, and the anion will be more stabl
e.
The sp orbitals of the C Hbonds of ethyne have 50% s character (because they ari
se from
the combination of one s orbital and one p orbital), those of the sp2 orbitals o
f ethene have
33.3% s character, while those of the sp3 orbitals of ethane have only 25% s cha
racter. This
means, in effect, that the sp carbon atoms of ethyne act as if they were more el
ectronegative
than the sp2 carbon atoms of ethene and the sp3 carbon atoms of ethane. (Remembe
r
Electronegativity measures an atoms ability to hold bonding electrons close to it
s nucleus,
and having electrons closer to the nucleus makes it more stable.)
The effect of hybridization on acidity is borne out in the calculated electrosta
tic potential
maps for ethyne, ethene, and ethane shown in Fig. 3.4. Some positive charge (ind
icated
9
C C
H
H
H
H
C C
H
H
H
H
H
H C C H H
Ethyne
pKa 25
Ethene
pKa 44
Ethane
pKa 50
Ethyne Ethene Ethane
Figure 3.4 Electrostatic
potential maps for ethyne,
ethene, and ethane.
118 Chapter 3 An Introduction to Organic Reactions and Their Mechanisms
by blue color) is clearly evident on the hydrogens of ethyne (pKa 25), but almos
t no positive
charge is present on the hydrogens of ethene and ethane (both having pKa values
more
than 20 units greater than ethyne). This is consistent with the effectively grea
ter electronegativity
of the sp orbitals in ethyne, which have more s character than the sp2 and sp3
orbitals in ethene and ethane. [Also evident in Fig. 3.4 is the negative charge
resulting from
electron density in the p bonds of ethyne and ethene (indicated by red in the re
gion of their
respective p bonds). Note the cylindrical symmetry of p electron density in the
triple bond
of ethyne. In the p bond of ethene there is a region of high electron density on
its underneath
face complementary to that visible on the top face of its double bond.]
Now we can see how the order of relative acidities of ethyne, ethene, and ethane
parallels
the effective electronegativity of the carbon atom in each compound
Relative Acidity of the Hydrocarbons
HC CH H2C CH2
H3C CH3
Being the most electronegative, the sp-hybridized carbon atom of ethyne polarize
s its
C Hbonds to the greatest extent, causing its hydrogens to be most positive. Ther
efore,
ethyne donates a proton to a base more readily. And, in the same way, the ethyni
de ion is
the weakest base because the more electronegative carbon of eethyne is best able
to stabilize
the negative charge.
Relative Basicity of the Carbanions
H3C CH2
: H2C CH: HC C:
Notice that the explanation given here involves electronegativity, just as that
given earlier
to account for the relative acidities of HF, H2O, NH3, and CH4.