Carbocation Stability

Although generations of organic chemists have used rates of

nucleophilic substitution reactions as a means of judging the stability of
carbocations, this approach is fraught with error.
o
Most 2 substrates do not react by the SN1 pathway
One is never sure of the extent to which cations that do form are
differentially stabilized by dipolar or more specific interactions
with the solvent

Two methodologies exist for more directly measuring carbocation

stabilities.

Formation of carbocations in hyperacid media, the discovery of

which won the Nobel for George Olah recently, allows us to study
the properties of carbocations.
o Ned Arnett has adapted this methodology to allow
measurement of the enthalpy of reaction for the process:

R-X R+ X-

in SbF5/FSO3H/SO2ClF at -40 oC.

o Some differences in the degree of ion pairing, and

therefore in solvation energies, undoubtedly exist, but the
results seem reasonable
Completely eliminating solvent can be accomplished by making
use of mass spectrometry, particularly ion cyclotron resonance.
One can, for example, measure the enthalpy of protonation of an
alkene to a carbocation, or the ionization of a free radical to a
carbocation.

Your textbook gives brief collections of data obtained in these ways.

The table below contains a more extensive selection. It also includes
for a few structures the 13C chemical shift of the carbocation carbon in
hyperacid media, which is very nearly invariant with structure.
Carbocation Hf, kcal/mol Hrxn, kcal/mol , 13C, ppm
CH3+ 261 not formed not formed
CH3CH2+ ** 216.2 not formed not formed
CH3CH2CH2+ ** 208 .... ....
(CH3)2CH+ 191.8 .... 320.6

176.7 .... ....

**
(CH3)3C+ 162.1 -35.5 335.2

154.6 -40.3 335.4

152.5 -36.7 336.4

(CH3CH2)3C+ 147.7 .... ....

226 .... ....

200 .... ....

183.8 .... ....

**

171 .... ....

164.2 -38.3 ....

152.7 -37.8 ....

187 .... ....

**

172 .... ....

 256 .... ....

211 .... ....

213 .... ....

**

200 .... ....

188 -40.3 ....

.... -39.3 199.4

213.6 -37.5 229.3

.... -49.0 ....

References for Carbocations

Gas Phase Enthapies of Formation
1. Aue and Bowers, "Gas Phase Ion Chemistry", ed. Bowers,
Academic Press, NY, 1979; Vol. 2, Chapter 3.
2. Kebarle, Angew. Chem. Int. Ed., 1979, 18, 951.
 3. Ridge, J. Am. Chem. Soc., 1979, 101, 4998
4. Traeger, J. Am. Chem. Soc., 1979, 101, 5791
5. Kebarle, J. Am. Chem. Soc., 1979, 101, 1084
6. Beauchamp, J. Am. Chem. Soc., 1979, 101, 1239
7. Trager, J. Am. Chem. Soc., 1981, 103, 3647
8. Ausloos, J. Am. Chem. Soc., 1980, 102, 2540.

Enthalpies of Reaction in Hyperacid Media

1. Arnett and Hofelich, J. Am. Chem. Soc., 1983, 105, 2889

2. Arnett, Petro, and Schleyer, J. Am. Chem. Soc., 1979, 101, 522
13
C Spectra of Carbocations

1. Nelson and Williams, Prog. Phys. Org. Chem., 1976, 12, 229.
2. Spiescecke and Schneider, Tetrahedron Lett., 1961, 468.
3. Olah and Mateescu, J. Am. Chem. Soc., 1970, 92, 1430
4. Olah and White, J. Am. Chem. Soc., 1969, 91, 3954
5. Hoffmann, J. Chem. Phys., 1964, 40, 2480

Ethyl Carbocation

1. Raghavachari, Whiteside, Pople, and Schleyer, J. Am. Chem.

Soc., 1981, 103, 5649
2. Ausloos, Rebbert, Sieck, and Tiernan, J. Am. Chem. Soc., 1972,
94, 8939

Cyclopentyl Carbocation

1. Schleyer, Carneiro, Koch, and Raghavachari, J. Am. Chem.

Soc., 1989, 111, 5475
2. Olah, "Carbocations and Electrophilic Reactions", John Wiley
and Sons, New York, 1974; p. 78
3. Saunders and Kates, J. Am. Chem. Soc., 1978, 100, 7082

2-Butyl Carbocation

1. Carneiro, Schleyer, Koch, and Raghavachari, J. Am. Chem.

Soc., 1990, 112, 4064
2. Clark and Harrison, Chem. Phys. Lett., 1981, 82, 143
 3. Saunders, Hagen, and Rosenfeld, J. Am. Chem. Soc., 1968, 90,
6882

Norboryl Carbocation

1. Myhre, Webb, and Yannoni, J. Am. Chem. Soc., 1990, 112, 8991
2. Johnson and Clark, J. Am. Chem. Soc., 1988, 110, 4112
3. Schleyer and Sieber, Angew. Chem. Int. Ed., 1993, 32, 1606

The Benzyl to Tropylium Rearrangement

1. Rylander and Meyerson, J. Am. Chem. Soc., 1956, 78, 5799

2. Rylander, Meyerson, and Grubb, J. Am. Chem. Soc., 1957, 79,
842
3. Meyerson and Rylander, J. Chem. Phys., 1957, 27, 901
4. Meyerson, Rylander, Eliel, and McCollum, J. Am. Chem. Soc.,
1959, 81, 2606
5. Pottie and Lossing, J. Am. Chem. Soc., 1961, 83, 2634