Carbocation Stability

1. Draw the structure of the methyl cation, CH3+. Describe the hybridization, geometry, and orbitals in this
species.

H
C

T he carbon here is sp2-hybridized, with trigonal planar geometry

( 120-degree bond angles) and a vacant 2p orbital on carbon.

2. Each of the following carbocations is significantly more stable than the methyl cation. Explain why each of
these species is especially stable. You should use both molecular orbital and resonance arguments in your
explanations.
resonance-stabilized
resonance-stabilized
H3C

H2
C CH2

H2C

( no resonance stabilization)
H

C
H

CH2

2pC
H2C

C-H

C
H

CH2

H3C

CH2

H3C

CH2

Hyperconjugation ( overlap of
H
2pC with the neighboring C-H )
H
helps to stabilize the carbocation;
the overlap is not particularly
Overlap of C-C with the
ef f ective but at least it makes it
vacant 2p orbital is more
more stable than the methyl
stabilizing than mere
cation!
hyperconjugation ( C-C is
a higher-energy donor
than C-H ).

H3C

T he lone pair electrons on

oxygen ( nO) are even higher
in energy than pC-C, thus are
even better donors to help
stabilize the carbocation.

3. Rank the above cations from least to most stable. Again, use both MO and resonance arguments to
explain the relative order of stability.
Since the energy of the f illed orbitals that overlap with the vacant 2p orbital on carbon is:
C-H

<

C-C

< nO

Then the stability of the carbocations themselves has the same ranking; in other words:

H3C

H2
C CH2

<

H2C

C
H

CH2

<

H3C

CH2

33

2014-06-05 15:25:00

1/2

Intro to Carbocations KEY.pdf (#2)

Carbocation Formation and Rearrangement

1. Each of the following alkyl halides can form a carbocation. Draw a curved arrow mechanism for the single
step of carbocation formation, and show the carbocation product.
Cl

Cl

Cl

2. Each of the following alkyl halides can form a carbocation. That carbocation can then rearrange to form a
more stable carbocation. Show a curved arrow mechanism for the protonation and rearrangement steps.
Make sure you understand why the rearrangement takes place!

Br

Br

2014-06-05 15:25:00

2/2

Intro to Carbocations KEY.pdf (2/2)