238

CH APT E R 6   The Reactions of Alkenes • The Stereochemistry of Addition Reactions

Alkyl groups stabilize carbocations because they decrease the concentration of positive charge
on the carbon. Notice that the blue area in the following electrostatic potential maps (representing
positive charge) is least intense for the most stable tert-butyl cation (a tertiary carbocation) and most
intense for the least stable methyl cation.

the most intense blue

indicates the carbon
with the highest
concentration of
positive charge

tert-butyl cation isopropyl cation ethyl cation methyl cation

Carbocation stability: 3° + 2° + 1°
Hyperconjugation
How do alkyl groups decrease the concentration of positive charge on the carbon? Recall that the
positive charge on a carbon signifies an empty p orbital (Section 1.10). Figure 6.1 shows that in the
ethyl cation, the orbital of an adjacent C ¬ H s bond (the orange orbital) can overlap the empty
p orbital (the purple orbital). This movement of electrons from a s bond orbital toward the vacant
p orbital decreases the charge on the sp2 carbon and causes a partial positive charge to develop on
the two atoms bonded by the overlapping s bond orbital (the H and the C). With three atoms shar-
ing the positive charge, the carbocation is stabilized because a charged species is more stable if its
charge is dispersed over more than one atom (Section 2.8). In contrast, the positive charge in the
methyl cation is concentrated solely on one atom.
+ hyperconjugation empty p orbital
d
H

s bond H H
orbital + +
d +
▶ Figure 6.1 C d
C the positive charge H C the positive charge is
Stabilization of a carbocation by H is shared by three concentrated on one
hyperconjugation. In the ethyl cation, the H atoms H atom
H
electrons of an adjacent C ¬ H S bond
orbital are delocalized into the empty p + +
orbital. Hyperconjugation cannot occur in CH3CH2 CH3
the methyl cation. ethyl cation methyl cation

Recall that delocalization of electrons by the overlap of a s bond orbital with an empty orbital
on an adjacent carbon is called hyperconjugation (Section 3.11). The molecular orbital diagram
in Figure 6.2 is another way of depicting the stabilization achieved by the overlap of a filled C ¬ H
s bond orbital with an empty p orbital.
empty p
orbital
increasing energy

filled s
bond
▶ Figure 6.2
A molecular orbital diagram showing the C H
stabilization achieved by overlapping the
electrons of a C ¬ H S bond orbital with an
empty p orbital.

Hyperconjugation occurs only if the orbital of the s bond and the empty p orbital have the proper
orientation. The proper orientation is easily achieved, though, because there is free rotation about
the carbon–carbon s bond (Section 3.11). Notice that the s bond orbitals that can overlap the empty
p orbital are those attached to an atom that is attached to the positively charged carbon. In the
tert-butyl cation, nine s bond orbitals can potentially overlap the empty p orbital of the positively
charged carbon. (The nine s bonds are indicated by red dots.)
 6.3  What Does the Structure of the Transition State Look Like?   239

H H
H H
H C H C H H H H H
H H
H C C+ H C C+ H C C+ H C C C+
each red dot H
indicates a s bond H C H H H H H H H
that can engage in H
hyperconjugation H
tert - butyl cation isopropyl cation ethyl cation propyl cation
tertiary secondary primary primary
carbocation carbocation carbocation carbocation

The isopropyl cation has six such s bond orbitals, whereas the ethyl and propyl cations each have
three. Therefore, hyperconjugation stabilizes the tertiary carbocation more than the secondary car-
bocation, and it stabilizes the secondary carbocation more than either of the primary carbocations.
Notice that both C ¬ H and C ¬ C s bond orbitals can overlap the empty p orbital.

PROBLEM 2 ♦
a. How many s bond orbitals are available for overlap with the vacant p orbital in the methyl cation?
b. Which is more stable: a methyl cation or an ethyl cation? Why?

PROBLEM 3 ♦
a. How many s bond orbitals are available for overlap with the vacant p orbital in
1.  the isobutyl cation?    2. the n-butyl cation?    3. the sec-butyl cation?
b. Which of the carbocations in part a is most stable?

PROBLEM 4 ♦
Rank the following carbocations in each set from most stable to least stable:
CH3
+ +
a. CH3CH2CCH3 CH3CH2CHCH3 CH3CH2CH2CH2
+          
+ + +
b. CH3CHCH2CH2 CH3CHCH2CH2 CH3CHCH2CH2
Cl     CH3     F

WHAT DOES THE STRUCTURE OF THE

6.3 TRANSITION STATE LOOK LIKE?
Now that we know that a tertiary carbocation is more stable than a primary carbocation, the next
question we need to answer is why the more stable carbocation is formed more rapidly.
We know that the rate of a reaction is determined by the free energy of activation—the difference
between the free energy of the transition state and the free energy of the reactant (Section 5.11).
Therefore, to understand how the stability of a carbocation affects the rate at which it is formed,
we need to understand how its stability affects the stability of the transition state for its formation.
If two points on the uphill leg or the downhill leg of a reaction coordinate diagram have similar
energies, they will also have similar structures—and the closer their energies, the more similar their
structures will be (Figure 6.1).

similar energies
similar structures
Free energy

Progress of the reaction