VOLUME 66, NUMBER 18 SEPTEMBER 7, 2001

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Perspective
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100 Years of Carbocations and Their Significance in Chemistry1

George A. Olah
Loker Hydrocarbon Research Institute and Department of Chemistry,
University of Southern California, Los Angeles, California 90089-1661

olah@[Link]

Received April 27, 2001

The centennial of the first report of a stable (persistent) acid. Triphenylmethyl chloride similarly formed orange
carbocation, the triphenylmethyl cation, serves as the complexes with aluminum and tin chlorides.
occasion to give a perspective based on recollections of Baeyer should be credited for having recognized in
my half century of their search. This included develop- 1902 the saltlike character of the compounds formed.5
ment of general methods to prepare persistent long-lived He then suggested a correlation between the appearance
carbocations in superacidic media, realization of the of color and salt formation, the so-called “halochromy.”
general concept of carbocations including trivalent and Gomberg (who had just shortly before discovered the
five or higher coordinated ions, as well delineation of related stable triphenylmethyl radical), as well as Walden,
their role and significance in chemistry. contributed to the evolving understanding of the struc-
ture of related cationic dyes such as malachite green.6
1. Early Studies of Triphenylmethyl Cations
Many elements readily form ionic compounds, for
example, sodium chloride in which the cationic sodium
and anionic chlorine are held together by electrostatic, Whereas the existence of ionic triarylmethyl and
ionic bonding. Carbon, however, was long considered to related dyes was thus established around the turn of the
lack the ability to form similar ionic compounds, except twentieth century, the more general significance of
in very specific, highly stabilized systems, such as tri- carbocations in chemistry long went unrecognized. Tri-
phenylmethyl dyes. arylmethyl cations were considered an isolated curiosity
The University of Chicago chemist Stieglitz, while of chemistry, not unlike Gomberg’s triarylmethyl radi-
studying salts of imido ethers, raised in 1899 the pos- cals. Not only were simple hydrocarbon cations believed
sibility of ionic hydrocarbon compounds.2 It was in 1901 to be unstable, even their fleeting existence was doubted.
that Norris,3 as well as Kehrman and Wentzel,4 inde-
pendently discovered that colorless triphenylmethyl al- 2. Kinetic and Stereochemical Studies Indicating
cohol gave deep yellow solutions in concentrated sulfuric Carbocations
One of the most original and significant ideas in
(1) Based in part on my Nobel Lecture Angew. Chem., Int. Ed. Engl. organic chemistry was the suggestion by Meerwein that
1995, 34, 1393, and my autobiographical reflections: A Life of Magic
Chemistry; Wiley-Interscience: New York, 2001.
(2) Stieglitz, J. Am. Chem. J. 1899, 21, 110. (5) Baeyer, A.; Villiger, V. Chem. Ber. 1901, 35, 1189; 3013.
(3) Norris, J. F. Am. Chem. J. 1901, 25, 117. (6) (a) Gomberg, M. Chem. Ber. 1902, 35, 2397. (b) Walden, P. Chem.
(4) Kehrmann, F.; Wentzel, F. Chem. Ber. 1901, 34, 3815. Ber. 1902, 35, 2018.

10.1021/jo010438x CCC: $20.00 © 2001 American Chemical Society

Published on Web 08/31/2001
5944 J. Org. Chem., Vol. 66, No. 18, 2001 Perspective

carbocations (as we now call all the positive ions of carbon trometry, the existence of gaseous carbocations was
compounds) might be intermediates to the course of proven, but this could not give an indication of their
reactions that start from nonionic reactants and lead to structure or allow extrapolation to solution chemistry.
nonionic covalent products. Direct observation and study of stable, long-lived carbo-
In 1922, Meerwein, while studying the Wagner re- cations, such as alkyl cations in the condensed state,
arrangement of camphene hydrochloride to isobornyl remained an elusive goal.
chloride with van Emster, found that the rate of the
reaction increased with the dielectric constant of the 3. My Search for Persistent, Long-Lived Alkyl
solvent.7 Furthermore, he found that certain Lewis acid Cations
chlorides such as SbCl5, SnCl4, FeCl3, AlCl3, and SbCl3
(but not BCl3 or SiCl4), as well as dry HCl, which promote My search for cationic carbon intermediates started in
the ionization of triphenylmethyl chloride by formation Hungary while I was studying Friedel-Crafts-type reac-
of carbocationic complexes, also considerably accelerated tions with acyl13 and subsequently alkyl fluorides cata-
the rearrangement of camphene hydrochloride to isobornyl lyzed by boron trifluoride.14 In the course of these studies,
chloride. Meerwein concluded that the isomerization I observed (and, in some cases, isolated) intermediate
actually does not proceed by way of migration of the complexes of either donor-acceptor or ionic nature.
chlorine atom but by a rearrangement of a cationic
intermediate. Hence, the modern concept of carbocationic
intermediates was born. Meerwein’s views were, how-
ever, greeted with much skepticism by his peers in
Germany, discouraging him from following up on these
studies.
The idea that ionization of alkyl fluorides to stable
alkyl cations could be possible with an excess of strong
Lewis acid fluoride that also serves as solvent first came
to me in the early 1950s while studying the boron
trifluoride-catalyzed alkylation of aromatics with alkyl
fluorides. In the course of these studies, I attempted to
isolate RF:BF3 complexes. Realizing the difficulty of
finding suitable solvents that would allow ionization but
at the same time would not react with developing,
potentially highly reactive alkyl cations, I condensed
alkyl fluorides with neat boron trifluoride at low tem-
peratures. I had, however, no access at the time to any
Ingold, Hughes, and their collaborators in England, modern spectrometers.
starting in the late 1920s, carried out detailed kinetic All I could do at the time with the RF-BF3 complexes
and stereochemical investigations on what became known was to measure their conductivity. The results showed
as nucleophilic substitution at saturated carbon and polar that methyl fluoride and ethyl fluoride complexes gave
elimination reactions.8 Their work relating to unimolecu- low conductivity, whereas the isopropyl fluoride and tert-
lar nucleophilic substitution and elimination, called SN1 butyl fluoride complexes were highly conducting.14 The
and El reactions, in which formation of carbocations is latter systems, however, also showed some polymeriza-
the slow rate-determining step, laid the foundation for tion (from deprotonation to the corresponding olefins).
the role of electron-deficient carbocationic intermediates The conductivity data thus must have been to some
in organic reactions. degree affected by acid formation.
In the United States in the 1930s, Frank Whitmore in
a series of papers generalized these concepts to include
many other organic reactions.9 Carbocations, however,
were generally considered to be unstable and transient
(short-lived) because they could not be directly observed. My work on long-lived (persistent) carbocations started
The concept of carbocations slowly grew to maturity in the late 1950s while I was working for Dow Chemical
through kinetic, stereochemical, and product studies of in Sarna, Ontario, Canada, and resulted in the first direct
a wide variety of reactions. Leading investigators such observation of alkyl cations.
as P. D. Bartlett, C. D. Nenitzescu, S. Winstein, D. J. In Friedel-Crafts chemistry, it was known that when
Cram, M. J. S. Dewar, J. D. Roberts, P. v. R. Schleyer, pivaloyl chloride is reacted with aromatics in the presence
and others contributed fundamentally to the development of aluminum chloride tert-butylated products are ob-
of modern carbocation chemistry. The role of carbocations tained in addition to the expected ketones. These were
as one of the basic concepts of modern chemistry has been assumed to be formed by decarbonylation of the inter-
well reviewed.10-12 With the advancement of mass spec- mediate pivaloyl complex or cation. In the late 1950s, I
returned to my earlier investigations of Friedel-Crafts
(7) Meerwein, H.; van Emster, K. Chem. Ber. 1922, 55, 2500. complexes and extended them by using IR and NMR
(8) Ingold, C. K. Structure and Mechanism in Organic Chemistry; spectroscopy. I studied isolable complexes of acyl fluoride
Cornell University Press: Ithaca, NY, 1953; and references therein;
2nd ed., 1969.
(9) Whitmore, F. C. J. Am. Chem. Soc. 1932, 54, 3274, 3276; Ann. (11) Bethell, D.; Gold, V. Carbonium Ions; Academic Press: London,
Rep. Prog. Chem. (Chem. Soc. London) 1933, 177; Chem. Eng. News New York, 1967.
1948, 26, 668. (12) Vogel, P. Carbocation Chemistry; Elsevier: Amsterdam, 1985.
(10) Olah, G. A., Schleyer, P.v. R., Eds. Carbonium Ions; Wiley- (13) Olah, G. A.; Kuhn, S. J. Chem. Ber. 1956, 89, 866.
Interscience: New York, 1968-76; Vols. I-V, and reviews therein. (14) Olah, G. A.; Kuhn, S. J.; Opal, J. J. Chem. Soc. 1957, 2174.
Perspective J. Org. Chem., Vol. 66, No. 18, 2001 5945

with Lewis acid fluorides, including higher-valence Lewis significantly deshielded from δ ∼1.5 to 4.3. This was very
acid fluorides such as SbF5, AsF5, and PF5.15-17 In the encouraging but not conclusive proof of the presence of
course of these studies, it was not entirely unexpected the tert-butyl cation. If one assumes that, with SbF5, tert-
that the generated (CH3)3CCOFSbF5 complex showed a butyl fluoride forms only a polarized donor-acceptor
substantial tendency toward decarbonylation. What was complex, which undergoes fast fluorine exchange (on the
exciting, however, was that it was possible to follow this NMR time scale), the fluorine-hydrogen coupling would
process by NMR spectroscopy and to observe what turned be “washed out,” while a significant deshielding of the
out to be the first stable, long-lived alkyl cation salt, methyl protons would still be expected. The differentia-
namely, tert-butyl hexafluoroantimonate. tion of a rapidly exchanging polarized donor-acceptor
complex from the long-sought-after ionic t-C4H9+ SbF6-
thus became a major challenge.

This breakthrough was first reported in 1962 and was

followed by further studies that led to methods for
preparing various long-lived alkyl cations in solution.
During a prolonged, comprehensive study of attempted Ned Baker, himself a physicist, showed great interest
ionization of alkyl halides, including fluoride with nu- in our chemical problem. To solve it, he devised a means
merous Lewis acid halides, I finally hit on antimony to obtain the carbon-13 NMR spectra of our dilute
pentafluoride. It turned out to be an extremely strong solutions, an extremely difficult task at the time before
Lewis acid and, for the first time, enabled the ionization the advent of Fourier transform NMR techniques. Label-
of alkyl fluorides to stable, long-lived alkyl cations. Neat ing with carbon-13 was possible at the time only to about
SbF5 solutions of alkyl fluorides are viscous, but when a 50% level (from Ba13CO3). When we prepared 50% 13C-
diluted with liquid sulfur dioxide the solutions could be labeled tert-butyl fluoride for ionization in SbF5, we could,
cooled and studied at -78 °C. Subsequently, I also however, obtain at best only a 5% carbocationic solution
introduced even lower-nucleophilicity solvents such as in SbF5. Thus, the 13C content in the ionic solution was
SO2ClF or SO2F2, which allowed studies at even lower 10-fold diluted. However, Baker, undaunted, devised
temperatures. Following the observation of the decar- what became known as the INDOR (internuclear double
bonylation of the pivaloyl cation that gave the first resonance) method. Using the high sensitivity of the
spectral evidence for the tertiary butyl cation, tert-butyl proton signal, he was able with the double-resonance
fluoride was ionized in excess antimony pentafluoride. technique to observe the 13C shifts of our dilute solutionss
The solution of the tert-butyl cation turned out to be a remarkable achievement around 1960. The carbon-13
remarkably stable, allowing chemical and spectroscopic shift of the tertiary carbon atom in (CH3)3CFSbF5 of 13C
studies alike.16,18 335.2 turned out to be more than 300 ppm deshielded
In the late 1950s, the research director of our labora- from that of the covalent starting material. Such very
tory was not yet convinced of the usefulness of NMR large chemical deshielding (the most deshielded 13C
spectroscopy. Consequently, we had no such instrumen- signal at the time) could not be reconciled with a donor-
tation of our own. Fortunately, the Dow laboratories in acceptor complex. It indicated rehybridization from sp3
Midland, MI, just 100 miles away, had excellent facilities to sp2 and at the same time showed the effect of
run by E. B. Baker, a pioneer of NMR spectroscopy, who significant positive charge on the carbocationic carbon
offered his help. To probe whether our SbF5 solution of center.
alkyl fluorides indeed contained alkyl cations, we rou- Besides the tert-butyl cation, we also succeeded in
tinely drove in the early morning to Midland with our preparing and studying the related isopropyl and the tert-
samples and watched Ned Baker obtain their NMR amyl cations. The isopropyl cation was of particular
spectra. tert- Butyl fluoride itself showed a characteristic relevance.
doublet in its 1H NMR spectrum due to the fluorine-
hydrogen coupling (JHF ) 20 Hz). In SbF5 solution, the
doublet disappeared and the methyl protons became

(15) Olah, G. A.; Kuhn, S. J.; Tolgyesi, W. S.; Baker, E. B. J. Am.

Chem. Soc. 1962, 84, 2733.
(16) Olah, G. A. Rev. Roum. Chim. (Buchrest) 1962, 7, 1129 Whereas in the tert-butyl cation the methyl protons are
(Nenitzescu issue). attached to carbons that are only adjacent to the carbo-
(17) Olah, G. A.; Tolgyesi, W. S.; Kuhn, S. J.; Moffatt, M. E.; Bastien, cationic center, in the isopropyl cation a proton is directly
I. J.; Baker, E. B. J. Am. Chem. Soc. 1963, 85, 1328.
(18) Preliminary communications and lectures: (a) Olah, G. A. attached to the center. When we obtained the proton
Conference Lecture at 9th Reaction Mechanism Conference, Brookhaven, NMR spectrum of the i-C3H7F-SbF5 system, the CH
NY, August 1962. (b) Olah, G. A. Abstracts, 142nd National Meeting
of the American Chemical Society, Atlantic City, NJ, Sep 1962;
proton showed up as an extremely deshielded septet at
American Chemical Society: Washington, DC, 1962; p 45. (c) Olah, G. 13.0 ppm, ruling out a polarized donor-acceptor complex
A.; Tolgyesi, W. S.; MacIntyre, J. S.; Bastien, I. J.; Meyer, M. W.; Baker, and indicating the formation of the (CH3)2CH+ ion. The
E. B. Abstracts A, XIX International Congress of Pure and Applied 13
Chemistry, London, June 1963; p 121. (d) Olah, G. A. Angew. Chem. C NMR spectrum was also conclusive, showing a very
1963, 75, 800. (e) Olah, G. A. American Chemical Society 1964 highly deshielded (by ∆δ > 300) +C atom (δ13C 320.6).
Petroleum Award Lecture, Reprints; Division of Petroleum Chemistry; The spectrum of the tert-amyl cation showed an ad-
American Chemical Society: Washington, DC, 1964; Vol. 9, No. 7, C31.
(f) Olah, G. A. Intermediate Complexes and Their Role in Electrophilic ditional interesting feature due to the strong long-range
Aromatic Substitutions; Conference Lecture at Organic Reaction H-H coupling of the methyl protons adjacent to the
Mechanism Conference, Cork, Ireland, June 1964; Special Publication carbocationic center with the methylene protons. If only
No. 19, The Chemical Society, London, 1965. (g) Olah, G. A.; Pittman,
C. U., Jr.. In Advances in Physical Organic Chemistry; Gold, V., Ed.; the donor-acceptor complex were involved, such long-
Academic Press: London, New York, 1966; Vol. 4, p 305. range coupling through an sp3 carbon would be small
5946 J. Org. Chem., Vol. 66, No. 18, 2001 Perspective

Figure 1. 1H NMR spectra of (a) the tert-butyl cation

[trimethylcarbenium ion, (CH3)3C+]; (b) the tert-amyl cation
[dimethylethylcarbenium ion, (CH3)3C+-C2H5]; and (c) the Figure 2. IR spectra of tert-butyl (top), isopropyl (center), and
isopropyl cation [dimethylcarbenium ion, (CH3)2C+H] (60 MHz, tert-amyl (bottom) cations. T ) transmission.
in SbF5/SO2ClF solution, -60 °C).
calculations of the spectra showed good agreement with
(1-2 Hz). Instead, the observed significant coupling (JH-H our early work. This was also an early example of the
) 10 Hz) indicated that the species studied indeed had realization that for nearly all carbocations there exists a
an sp2 center through which the long-range H-H cou- neutral isoelectronic isostructural boron analogue, which
pling became effective. Figure 1 reproduces the 1H NMR later proved itself so useful in the hands of my colleagues
spectra of the tert-butyl, tert-amyl, and isopropyl cations. Williams, Prakash, and Field.
These original spectra are framed and hang in my office The chemistry of stable, long-lived (or persistent)
as a memento, as are the ESCA spectra of the tert-butyl carbocations, as they became known, thus began. Many
and of the norbornyl cation (vide infra).19 have since contributed to the study of long-lived carbo-
IR spectroscopic studies on tert-butyl cation was also cations. The field rapidly expanded and allowed success-
carried out in neat SbF5 at room-temperature long before ful study of practically any carbocationic system. My
the advent of the Fourier transform methods. Subse- talented and hard-working former associates and stu-
quently, in 1968-1970, with DeMember and Commeyras dents deserve the lion’s share of credit for our work, as
in Cleveland,20 we were able to carry out more detailed do the many researchers around the world who joined in
IR and laser Raman spectroscopic studies of alkyl cations. and contributed so much to the development of the field
Comparison of the data of unlabeled and deuterated tert- (their work can be found in the references). I would like,
butyl cations with those of isoelectronic trimethylboron however, to mention particularly the pioneering work of
proved the planar structure of the carbocation. Brouwer and Hogeveen,22 as well as their colleagues at
the Shell Laboratories in Amsterdam in the 1960s and
1970s. They contributed fundamentally to the study of
long-lived carbocations and related superacidic hydro-
carbon chemistry. The first publication from the Shell
laboratories on alkyl cations appeared in 1964, following
closely my initial reports of 1962-1963.
Our studies also included IR spectroscopic investiga- Subsequent to my study of alkyl cations, a wide
tion of the observed ions (Figure 2). John Evans, who was spectrum of carbocations as long-lived species was stud-
at the time a spectroscopist at the Midland Dow labora- ied using antimony pentafluoride as an extremely strong
tories, offered his cooperation and was able to obtain and Lewis acid and later using other highly acidic (super-
analyze the vibrational spectra of our alkyl cations. It is acidic) systems.
rewarding that, some 30 years later, FT-IR spectra ob- Until this time, alkyl cations were considered only
tained by Sunko and his colleagues in Zagreb21 with low- transient species. Their existence had been indirectly
temperature matrix-deposition techniques and Schleyer’s
(20) Olah, G. A.; DeMember, J. R.; Commeyras, A.; Bribes, J. L. J.
(19) (a) Olah, G. A.; Baker, E. B.; Evans, J. C.; Tolgyesi, W. S.; Am. Chem. Soc. 1971, 93, 459 and references therein.
McIntyre, J. S.; Bastien, I. J. J. Am. Chem. Soc. 1964, 86, 1360. (b) (21) Vancik, H.; Sunko, D. E. J. Am. Chem. Soc. 1989, 111, 3742.
Olah, G. A. Chem. Eng. News 1967, 45, 76; Science 1970, 168, 1798. (22) Brouwer, D. M.; Mackor, E. L. Proc. Chem. Soc. 1964, 147.
Perspective J. Org. Chem., Vol. 66, No. 18, 2001 5947

inferred from kinetic and stereochemical studies, but no strong acid systemssmany billions or even trillions of
reliable spectroscopic or other physical measurements of times stronger than sulfuric acidshave been discovered.
simple alkyl cations in solution or in the solid state had The acidity of aqueous acids is generally expressed by
been obtained. their pH, which is a logarithmic scale of the hydrogen
ion concentration (or, more precisely, of the hydrogen ion
4. The Role of Superacids activity). pH can be measured by the potential of a
hydrogen electrode in equilibrium with a dilute acid
It was not fully realized until my breakthrough using solution or by a series of colored indicators. In highly
extremely strong superacids that, to suppress the depro- concentrated acid solutions or with strong nonaqueous
tonation of alkyl cations to olefins and the subsequent acids, the pH concept is no longer applicable, and acidity,
formation of complex mixtures by reactions of olefins with for example, can be related to the degree of transforma-
alkyl cations, such as alkylation, oligomerization, poly- tion of a base to its conjugate acid (keeping in mind that
merization, and cyclization, acids much stronger than this will depend on the base itself). The widely used so-
those known and used in the past were needed. called Hammett acidity function Ho relates to the half-
protonation equilibrium of suitable weak bases. The
Hammett acidity function is also a logarithmic scale on
which 100% sulfuric acid has a value of Ho -11.9. The
acidity of sulfuric acid can be increased by the addition
Finding such acids (called “superacids”)23 turned out
of SO3 (oleum). The Ho of HF is -11.0 (however, when
to be the key to obtaining stable, long-lived alkyl cations
HF is completely anhydrous, its Ho is - 15, but even a
and, in general, carbocations. If any deprotonation were
slight amount of water drops the acidity to -11, as shown
still to take place, the formed alkyl cation (a strong Lewis
by Gillespie).
acid) would immediately react with the formed olefin (a
Perchloric acid (HClO4; Ho -13.0), fluorosulfuric acid
good π-base), leading to the mentioned complex reactions.
(FSO3H; Ho -15.1), and trifluoromethanesulfonic acid
In the course of my studies, it became increasingly (CF3SO3H; Ho -14. 1) are considered to be superacids,
clear that a variety of highly acidic systems besides the as is truly anhydrous hydrogen fluoride. Complexing with
originally used antimony pentafluoride systems are Lewis acidic metal fluorides of higher valence, such as
capable of generating long-lived, stable carbocations. The antimony, tantalum, or niobium pentafluoride, greatly
work was thus extended to a variety of other superacids. enhances the acidity of all these acids.
Protic superacids such as FSO3H (fluorosulfuric acid) and In the 1960s, Gillespie suggested calling protic acids
CF3SO3H (triflic acid) as well as conjugate acids such as stronger than 100% sulfuric acid “superacids.” This
HF-SbF5, FSO3H-SbF5 (magic acid), CF3SO3H-SbF5, arbitrary but most useful definition is now generally
and CF3SO3H-B(O3SCF3)3 were extensively used. Super- accepted. It should be mentioned, however, that the name
acids based on Lewis acid fluorides such as AsF5, TaF5, “superacid” goes back to J. B. Conant of Harvard, who
and NbF5 and other strong Lewis acids such as used it in 1927 in a paper in the Journal of the American
B(O3SCF3)3 were also successfully introduced. The name Chemical Society to denote acids such as perchloric acid,
“magic acid” for the FSO3H-SbF5 system was given by which he found stronger than conventional mineral acids
Joe Lukas, a German postdoctoral fellow working with and capable of protonating such weak bases as carbonyl
me in Cleveland in the 1960s, who after a laboratory compounds.25 My book on superacids, published in 1985
Christmas party put remainders of a candle into the acid. with Surya Prakash and Jean Sommer,23c was ap-
The candle dissolved, and the resulting solution gave a propriately dedicated to the memory of Conant. Few of
clear NMR spectrum of the tert-butyl cation. This obser- today’s chemists are aware of his contributions to this
vation understandably evoked much interest, and the field. Conant subsequently became the president of
acid used was named “magic.” The name stuck in our Harvard University and gave up chemistry, which may
laboratory. I think it was Ned Arnett who learned about explain why he never followed up on his initial work on
it during one of his visits and subsequently introduced superacids.
the name into the literature, where it became quite
In a generalized sense, acids are electron-pair accep-
generally used.
tors. They include both protic (Bronsted) acids and Lewis
I would like to credit especially the fundamental acids such as AlC13 and BF3 that have an electron-
contributions of Ron Gillespie to the inorganic chemistry deficient central metal atom. In extending the concept
of strong acids (superacids),23a,b which greatly contributed of superacidity to Lewis acid halides, those stronger than
to the development of superacid chemistry. His long- anhydrous aluminum chloride (the most commonly used
standing interest in fluorosulfuric acid and our studies Friedel-Crafts acid) are considered super Lewis acids.
of SbF5-containing systems thus found common ground These superacidic Lewis acids include higher-valence
in studies of FSO3H-SbF5 (magic acid) systems.24 fluorides such as antimony, arsenic, tantalum, niobium,
Until the late 1950s, chemists generally considered and bismuth pentafluorides. Superacidity encompasses
mineral acids, such as sulfuric, nitric, perchloric, and both very strong Bronsted and Lewis acids and their
hydrofluoric acids, to be the strongest acid systems in conjugate acid systems.
existence. This has changed considerably as extremely Friedel-Crafts Lewis acid halides form with proton
donors such as H2O, HCl, and HF conjugate acids such
(23) (a) Gillespie, R. J. Acc. Chem. Res. 1968, 1, 202. (b) Gillespie, as H2O‚BF3, HCl-AlC13, and HF-BF3, which ionize to
R. J.; Peel, T. E. Adv. Phys. Org. Chem. 1972, 9, 1; J. Am. Chem. Soc.
1973, 95, 5173. (c) Olah, G. A.; Prakash, G. K. S.; Sommer, J. H3O+BF3OH-, H2Cl+AlCl4-, and H2F+BF4-, etc. These
Superacids; Wiley: New York, 1985. (d) Gillespie, R. J. Can. Chem. conjugate Friedel-Crafts acids have Ho values from
News 1991, May, 20. about -14 to -16. Thus, they are much stronger than
(24) (a) Bacon, J.; Dean, P. A. W.; Gillespie, R. J. Can. J. Chem.
1969, 47, 1655. (b) Olah, G. A.; Calin, M. J. Am. Chem. Soc. 1968, 90,
938. (25) Hall, N. F.; Conant, J. B. J. Am. Chem. Soc. 1927, 49, 3047.
5948 J. Org. Chem., Vol. 66, No. 18, 2001 Perspective

the usual mineral acids. Even stronger superacid systems using various very strong acid systems (see discussion
are HSO3F-SbF5 (magic acid), HF-SbF5 (fluoroanti- of superacids) and low nucleophilicity solvents (SO2,
monic acid), and CF3SO3H-B(O3SCF3)3 (triflatoboric SO2CIF, SO2F2, etc.).26 A variety of precursors could be
acid). The acidity of anhydrous HF, HSO3F, and CF3SO3H used under appropriate conditions, as shown, for ex-
increases drastically upon addition of Lewis acid fluorides ample, in the preparation of the methylcyclopentyl cation.
such as SbF5, which form large complex fluoroanions
facilitating dispersal of the negative charge.

The acidity function of HSO3F increases on addition

of SbF5 from -15.1 to -23.0, the acidity of 1:1 FSO3H-
SbF5 (magic acid). Fluoroantimonic acid is even stronger;
with 4 mol % SbF5, the Ho value for HF-SbF5 is already
-21.0, a thousand times stronger than the value for
fluorosulfuric acid with the same SbF5 concentration. The
acidity of the 1:1 HF-SbF5 system or those with even
higher SbF5 concentrations reaches Ho -28. Thus, these
superacidic systems can be 1016 times stronger than 100%
sulfuric acid! (A trillion is 1012.)
Related superacid systems in which SbF5 is replaced
by AsF5, TaF5, NbF5, etc. are of somewhat lower acidity
A wide variety of carbocations and carbodications,
but are still extremely strong acids. So is HF-BF3, a very
including those that are aromatically stabilized as well
useful superacid that will not cause oxidative side reac-
those as stabilized by heteroatoms, were reported in the
tions. Ternary superacid systems including, for example,
nearly 200 publications on the topic during my Cleveland
FSO3H-HF or CF3SO3H-HF with Lewis acid fluorides
years.
are also known and used.
Acids are not limited to liquid (or gaseous) systems.
Solid acids also play a significant role. Acidic oxides such
as silica, silica-alumina, etc. are used extensively as solid
acid catalysts. New solid acid systems that are stronger
than those used conventionally are sometimes called solid
superacids. However, it must be kept in mind that when
carbocations are developing on solid surfaces or zeolitic
systems they will coordinate (bind) to nucleophilic sites
(oxygen, etc.), and thus only highly stable carbocations
will be observable as persistent species on such systems.
This of course does not mean that at the involved higher
temperatures some equilibrium with carbocationic spe-
cies could not exist provoking carbocationic reactions.
Solid perfluorinated resin sulfonic acid catalysts, such
as those based on the acid form of DuPont’s Nafion
ionomer membrane resin, and some higher perfluoro-
alkanesulfonic acids, such as perfluorodecanesulfonic
acid, more closely resemble liquid fluorinated superacids.

5. Generalization of the Study of Carbocations

After returning to academia in Cleveland in 1965, my
research continued and extended the study of carbo-
cations in varied superacidic systems as well as explora-
tion of the broader chemistry of superacids, involving During my Cleveland years, in 1969 I organized a
varied ionic systems and reagents. In Cleveland, a main symposium on carbocation chemistry. It was attended by
aspect of my research was directed to the exploration of many of the major investigators in the field (Nenitzescu,
the chemistry of these persistent cations of carbon Brown, Winstein, Dewar, Schleyer, Gillespie, Saunders,
compounds (carbocations) and the fascinating new area and others). We had lively discussion as was the case at
of chemistry opened up by superacids. Particular interest the symposium in the fall of 1977 after my move to Los
was generated as a great variety of carbocations were Angeles at USC and at a number of symposia I attended
found to be readily generated and studied in these in different locations such as at La Grand Motte (France),
enormously strong acid systems. Bangor (U.K.), and eventually Seattle, WA.
Over a decade of research, we were able to show that
(26) Olah, G. A. Angew. Chem., Intl. Ind. 1973, 12, 173; Angew.
practically all conceivable carbocations could be prepared Chem. 1973, 85, 183. Olah, G. A. Carbocations and Electrophilic
under what became known as “stable ion conditions” Reactions; Verlag Chemie:Weinheim, Wiley: New York, 1974.
Perspective J. Org. Chem., Vol. 66, No. 18, 2001 5949

6. The Nonclassical Ion Controversy and Its the results of the extensive solvolytic studies, he sug-
Significance gested that high exo/endo rate and product ratios do not
necessitate σ-participation as an explanation. In other
During the study of carbocations, much effort was put words, exo is not fast; endo is slow. His suggestion for
into studying whether certain carbocations represent the structure of the norbornyl cation was that of a rapidly
rapidly equilibrating trivalent carbenium ions or static equilibrating pair of regular trivalent ions (classical ions),
(bridged, delocalized) five-coordinate carbonium ion sys- and he compared the process to that of a windshield
tems. This question became the focus of the rather wiper. However, at the same time, none of his studies
headed controversy which centered around the question ever showed that σ-participation cannot be involved.
of the norbornyl cation and became known as the In 1962, H. C. Brown lodged his dissent against the
nonclassical ion controversy.27 σ-bridged 2-norbornyl cation and, for that matter, other
The controversy in which I was inadvertently involved nonclassical carbocations. He has maintained his position
started over the structure of a deceptively simple seven- virtually unchanged over the years and has continued
carbon-containing bicyclic carbocation, the 2-norbornyl to present his views forcefully. In arguing against carbon
(bicyclo[2.2.1]heptyl) cation. The involvement of the ion σ-bridging, he took the position, despite his pioneering
in the long-recognized rearrangement of norbornyl sys- work in structurally closely related boranes, that if
tems prevalent in natural terpenes was first suggested carbon were to participate in bridging, novel bonding
in 1922 by Meerwein. The remarkable facility of skeletal characteristics must be attributed to it.
rearrangements in norbornyl systems attracted the early In 1965, he stated, “On the other hand, the norbornyl
interest of chemists. Wagner realized first in 1899 the cation does not possess sufficient electrons to provide a
general nature of these rearrangements and related them pair for all of the bonds required by the proposed bridged
to that which takes place during the dehydration of structures. One must propose a new bonding concept, not
pinacolyl alcohol to tetramethylethylene. Sommer later yet established in carbon structures” (with my emphasis
found some tricyclanes in the products of the Wagner added).
rearrangements of terpenes. In 1918, Ruzicka suggested In 1967, he again wrote, “The second subclass consists
a tricyclane-type mechanism without realizing the ionic of ions such as the bicyclobutonium and the norbornyl
nature of the process. Meerwein reconsidered the mech- cation in its σ-bridging form, which do not possess
anism in 1922 and made the farsighted suggestion that sufficient electrons to provide a pair for all of the bonds
the reaction proceeds through an ionic intermediate, i.e., required by the proposed structures. A new bonding
the norbornyl cation. Hence, this type of transformation concept not yet established in carbon structures is re-
is now known as the Wagner-Meerwein rearrangement. quired” (emphasis added).
The structure of the norbornyl cation became contro- The Brown-Winstein nonclassical ion controversy can
versial in the “nonclassical ion” controversy following be summed up as differing explanations of the same
Wilson’s original suggestion in 1939 of a mesomeric, experimental facts (which were obtained repeatedly and
R-delocalized, carbocationic intermediate in the cam- have not been questioned) of the observed significantly
phene hvdrochloride-isobornyl chloride rearrangement. higher rate of the hydrolysis of the 2-exo- over the 2-endo-
From 1949 to 1952, Winstein and Trifan reported a solvo- norbornyl esters. As suggested by Winstein, the reason
lytic study of the exo- and endo-2-norbornyl brosylates for this is participation of the C1-C6 single bond leading
(p-bromobenzenesulfonates) and postulated a σ-delocal- to delocalization via the bridged “nonclassical” ion. In
ized, symmetrically bridged norbornyl ion intermediate. contrast, Brown maintained that the cause was only
The endo reactant was found to solvolyze in various steric hindrance to the sterically hindered endo side
solvents such as acetic acid, aqueous acetone, and aque- involving rapidly equilibrating “classical” trivalent ions.
ous dioxane to give substitution products of exclusively Nonclassical ions, a term first used by John Roberts,28
exo configuration. The exo-brosylate also gave exclusively were defined by Paul Bartlett as containing too few
exo product and was markedly more reactive in acetolysis electrons to allow a pair for each “bond”; i.e., they must
than the endo, by a factor of 350. contain delocalized σ-electrons.27a This is where the
Winstein, one of the most brilliant chemists of his time, question stood in the early 1960s. The structure of the
concluded that “it is attractive to account for these results intermediate 2-norbornyl ion could only be suggested
by way of the bridged (nonclassical) formulation for the indirectly from rate (kinetic) data and observation of
norbornyl cation involving accelerated rate of formation stereochemistry; no direct observation or structural study
from the exo precursor [by anchimeric assistance].” His was possible at the time.
formulation of the norbornyl cation as a σ-bridged species My own involvement with the norbornyl ion contro-
stimulated other workers in the solvolysis field to inter- versy goes back to 1960-1962, when, as discussed, I
pret results in a variety of systems in similar terms of succeeded in developing a general method of preparing
σ-delocalized, bridged carbonium ions. and studying persistent (long-lived) alkyl cations. My
H. C. Brown (the outstanding pioneer of hydroboration interest subsequently extended to the study of various
chemistry), in contrast, concluded that in solvolysis both carbocations, including the controversial 2-norbornyl
2-exo- and 2-endo-norbornyl esters (brosylates, etc.) cation. Whereas previous investigators were able to study
undergo anchimerically unassisted ionization and that carbocations only indirectly (by kinetic and stereochem-
the singular rate and product characteristics of the ical studies), my newly discovered methods allowed their
system are attributable to steric effects, in particular, preparation and direct study as persistent (long-lived)
hindrance to ionization of the endo isomers. Explaining species.
At the 1962 Brookhaven Mechanism Conference, where
(27) (a) Bartlett, P. D. Nonclassical Ions; W. A. Benjamin: New York, I first reported on long-lived carbocations in public, I was
1965. (b) Winstein, S. Quart. Rev. (London) 1969, 23, 1411. (c) Brown,
H. C. (with commentary by P. v. R. Schleyer) The Nonclassical Ion
Problem; Plenum Press: New York, 1977; and references therein. (28) Roberts, J. D.; Mazur, R. H. J. Am. Chem. Soc. 1951, 73, 3542.
5950 J. Org. Chem., Vol. 66, No. 18, 2001 Perspective

Figure 3. Left: 395 MHz 1H NMR spectra of the 2-norbornyl cation in SbF5/SO2ClF/SO2F2 solution. Right: 50 MHz proton
decoupled13C NMR spectra of the 2-norbornyl cation (13C enriched) in SbF5/SO2ClF/SO2F2 solution.

called aside separately by Winstein and Brown, both routes (representing σ-, π-, or bent σ-participation) gave
towering and dominating personalities of the time who the identical ion.
cautioned me that a young man should be exceedingly As mentioned, we were able to obtain NMR spectra of
careful in making such claims. Each pointed out that the norbornyl ion at -78 °C, where the 3,2-hydride shift
most probably I was wrong and could not have obtained was frozen out. However, it took until 1969, after my
long-lived carbocations. Just in case, however, my method move to Cleveland, to develop more efficient low-tem-
turned out to be real, I was advised to obtain further perature techniques using solvents such as SO2ClF and
evidence for the “nonclassical” or “classical” nature SO2F2. We were eventually able to obtain high-resolution
(depending on who was giving the advice) of the much- 1H and 13C NMR spectra (using 13C-enriched precursor)

disputed 2-norbornyl cation. of the 2-norbornyl cation down to -159 °C (Figure 3).31
Because my method indeed allowed me to prepare Both the 1,2,6-hydride shifts and the Wagner-Meerwein
practically any carbocation as long-lived species, clearly rearrangement were frozen out at such a low tempera-
the opportunity was there to experimentally decide the ture, allowing us to observe the static, bridged ion, which
norbornyl ion question through direct observation of the I first reported at the Salt Lake City Organic Symposium
ion. At the time of the Brookhaven conference, I had in 1969.
already obtained the proton NMR spectrum of 2-nor- The differentiation of bridged nonclassical from rapidly
bornyl fluoride in SbF5, but only at room temperature, equilibrating classical carbocations based on NMR spec-
which displayed a single broad peak indicating com- troscopy was difficult because NMR is a relatively slow
plete equilibration through hydride shifts and Wagner- physical method. We addressed this question in our work
Meerwein rearrangement (well-known in solvolysis stud- using estimated NMR shifts of the two structurally
ies and related transformations of 2-norbornyl systems). differing ions in comparison with model systems. Later,
However, my curiosity was aroused, and when I moved this task became greatly simplified and more precise by
to Dow’s Research Laboratory in the Boston area in 1964, highly efficient calculational methods such as IGLO and
the work was further pursued in cooperation with Paul
Schleyer from Princeton (who became a lifetime friend) (29) Saunders, M.; Schleyer, P. v. R.; Olah, G. A. J. Am. Chem. Soc.
and Martin Saunders from Yale.29 Using SO2 as solvent, 1964, 86, 5680.
(30) (a) Olah, G. A.; White, A. M.; DeMember, J. R.; Commeyras,
we were able to lower the temperature of the solution to A.; Lui, C. Y. J. Am. Chem. Soc. 1970, 92, 4627. (b) Olah, G. A.;
-78 °C, and we also prepared the ion by ionization of Prakash, G. K. S.; Arvanaghi, M.; Anet, F. A. L. J. Am. Chem. Soc.
â-cyclopentenylethyl fluoride or by protonation of nortri- 1982, 104, 7105.
(31) (a) Olah, G. A.; Mateescu, G. D.; Wilson, L. A.; Gross, M. H. J.
cylene in FSO3H; SbF5/SO2ClF.30 The three separate Am. Chem. Soc. 1970, 92, 7231. (b) Olah, G. A.; Mateescu, G. D.;
Riemenschneider, J. L. J. Am. Chem. Soc. 1972, 94, 2529. (c) Johnson,
S. A.; Clark, D. T. J. Am. Chem. Soc. 1988, 110, 4112.
(32) Arnett, E. M.; Pienta, N.; Petro, C. J. Am. Chem. Soc. 1980,
102, 398.
(33) Saunders, M.; Kates, M. R. J. Am. Chem. Soc. 1980, 102, 6867.
(34) Yannoni, C. S.; Macho, V.; Myhre, P. C. J. Am. Chem. Soc. 1982,
104, 7380.
(35) Laube, T. Angew. Chem. 1987, 99, 580; Angew Chem., Int. Ed.
Engl. 1987, 26, 560.
(36) Schleyer, P. v. R.; Sieber, S. Angew Chem. 1993, 105, 1676;
Angew. Chem., Int. Ed. Engl. 1993, 32, 1606 and references therein.
(37) Olah, G. A.; Prakash, G. K. S.; Saunders, M. Acc. Chem. Res.
1983, 16, 440.
(38) Bekesy, G. V. Experiments in Hearing; McGraw-Hill: New York,
1960; p 8.
Perspective J. Org. Chem., Vol. 66, No. 18, 2001 5951

nature of the 2-norbornyl cation.36 The classical 2-nor-

bornyl cation was not even found to be a high-lying
intermediate!
As the norbornyl ion controversy evolved, it became a
highly public and increasingly personal and sometimes
even bitter public debate. Saul Winstein unexpectedly
died in the fall of 1969, shortly after the Salt Lake City
symposium. To my regret, I seemed to have inherited his
role in representing the bridged nonclassical ion concept
in subsequent discussions.
The 1983 Seattle American Chemical Society sympo-
sium was the de facto “closing” of the long-running
debate. Although in the heat of the debates some personal
remarks were made on both sides (to which I subse-
quently expressed my regret), the experimental evidence
at the time was already so overwhelming that I concluded
my presentation saying, “I do not intend to do any more
research on the matter. There is nothing further to be
Figure 4. Left: carbon 1s photoelectron spectrum of the tert- discussed...”. My lecture was subsequently published
butyl cation (top curve from experiment; bottom curve calcu- (with Prakash and Saunders) under the title “Conclusion
lated). Right: 1s core-hole-state spectra for the 2-norbornyl of the Classical-Nonclassical Ion Controversy Based on
cation (top), Clark’s simulated spectra for the classical (center), the Structural Study of the 2-Norbornyl Cation” in an
and nonclassical ions (bottom).
article in Accounts of Chemical Research.37 In the same
issue, Brown wrote, “The nonclassical theory is not
GIAO, allowing the calculation of NMR shifts of differing necessarily wrong, but it has been too readily accepted”
ions and their comparison with experimental data. It is (probably an understatement concerning the enormous
rewarding to see, however, that our earlier results and amount of work carried out on the topic). In any case, I
conclusions stood up well against all the more recent kept my promise and have not done further work in the
advanced studies. field. The chemical community seems to have accepted
Siegbahn’s core electron spectroscopy (ESCA) was the closure of the debate. This is the way the much-
another fast physical method that we applied to further publicized so-called nonclassical ion controversy ended.
resolve the question of bridged versus rapidly equilibrat- To summarize, it basically centered on the question of
ing ions. We were able to study carbocations in the late whether the structure of carbocations, including rapidly
1960s by this method, adapting it to superacidic matrixes. equilibrating “classical” ions, can be depicted adequately
George Mateescu and Louise Riemenschneider in my by using only Lewis-type two-electron two-center covalent
Cleveland laboratory set up the necessary instrumenta- bonding or whether there are also bridged or σ-localized
tion and methodology for obtaining the ESCA spectra of ions, whose structural depiction necessitates two-electron
a number of carbocations, including the tert-butyl and three-center bonding of the involved higher-coordinate
the 2-norbornyl cation in SbF5-based superacidic ma- carbon. The outcome was a new understanding of the
trixes.31 These studies again convincingly showed the general bonding nature of carbon compounds and the
nonclassical nature of the 2-norbornyl cation. No trivalent electron-donor ability and reactivity of single bonds of
carbenium center characteristic of a “classical” ion, such saturated hydrocarbons and σ-bond in general in elec-
as is the case for the tert-butyl cation, was observed in trophilic reaction.
the ESCA spectrum on a time scale where no chemical Intensive, critical studies of controversial topics also
equilibration process could have any effect. Subsequent helps to eliminate the possibility of errors. One of my
ESCA studies in cooperation with Grunthaner’s labora- favorite quotations is by George Bekesy, a fellow Hun-
tory at Caltech’s Jet Propulsion Laboratory and by Dave garian-born physicist who studied questions of the inner
Clark in England fully justified our initial results and ear and hearing (Nobel Prize in medicine, 1961):38
conclusions (Figure 4). So did the results of ever more
advanced theoretical calculations. “[One] way of dealing with errors is to have
Additional significant experimental studies were also friends who are willing to spend the time neces-
carried out by other laboratories. Arnett reported fun- sary to carry out a critical examination of the
damental calorimetric studies.32 Saunders showed the experimental design beforehand and the results
absence of deuterium isotopic perturbation of equilibrium after the experiments have been completed. An
expected for a classical equilibrating system.33 Myhre and even better way is to have an enemy. An enemy
Yannoni, at extremely low (5 K) temperature, were able is willing to devote a vast amount of time and
to obtain solid-state 13C NMR spectra that still showed brain power to ferreting out errors both large and
no indication of freezing out any equilibrating classical small, and this without any compensation. An-
ions. The barrier at this temperature should be as low other trouble with enemies is that they sometimes
as 0.2 kcal/mol (i.e., about the energy of a vibrational develop into friends and lose a good deal of their
transition).34 Laube was able to carry out single-crystal zeal. It was in this way the writer lost his three
X-ray structural studies on substituted 2-norbornyl cat- best enemies. Everyone, not just scientists, need
ions.35 Schleyer’s advanced theoretical studies including a few good enemies!”
IGLO and related calculation of NMR shifts and their
comparison with experimental data contributed further Clearly, there was no lack of devoted adversaries
to the understanding of the σ-bridged carbonium ion (perhaps a more proper term than enemies) on both sides
5952 J. Org. Chem., Vol. 66, No. 18, 2001 Perspective

of the norbornyl ion controversy. It is to their credit that center always has eight valence electrons, but overall
we today probably know more about the structure of carbonium ions are electron deficient because of the
carbocations, such as the norbornyl cation, than about sharing of two electrons among three (or more) atoms.
most other chemical species. Their efforts also resulted CH5+ can be considered the parent for carbonium ions.
not only in rigorous studies but also in the development Lewis’ concept that a covalent chemical bond consists
or improvement of many techniques. Although many of a pair of electrons shared between two atoms is a
believe that too much effort was expended on the “futile” cornerstone of structural chemistry. Chemists tend to
norbornyl ion controversy, I am convinced that it eventu- brand compounds as anomalous whose structures cannot
ally resulted in significant new insights and consequences be depicted in terms of such valence bonds alone. Carbo-
to chemistry. It affected in a fundamental way our cations with too few electrons to allow a pair for each
understanding of the chemical bonding of electron- “bond” came to be referred to as “nonclassical,” a name
deficient carbon compounds, extending Kekule’s concept as mentioned first used by Roberts for the cyclopropyl-
of the limiting ability of carbon to associate with no more carbinyl cation and adapted by Winstein for the nor-
than four other atoms or groups. An equally significant bornyl cation.43 The name is still used, even though it is
consequence of the norbornyl cation studies was that I now recognized that, like other compounds, they adopt
was able to realize the ability of saturated C-H and C-C
the structures appropriate for the number of electrons
single bonds to act in general as σ-electron donors toward
they contain with two-electron three (even multi)-center
strong electrophiles such as carbocations or other highly
bonding, not unlike the bonding principle established by
reactive reagents in superacidic systems, not only in
Lipscomb for boron compounds.42 The prefixes “classical”
intramolecular but also in intermolecular reactions. The
and “nonclassical,” I believe, will gradually fade away as
key for this reactivity lies in the ability to form two-
the general principles of bonding are recognized more
electron three-center (2e-3c) bonds (familiar in boron and
widely.
organometallic chemistry). The electrophilic chemistry of
saturated hydrocarbons (including that of the parent
methane) rapidly evolved based on the recognition of the
concept of hypercoordinate, in short, hypercarbon chem-
istry.39

7. The General Concept of Carbocations

Once the direct observation of stable, long-lived carbo-

cations generated in highly acidic (superacid) systems Concerning carbocations, previous usage named the
became possible, it led me to the recognition of the trivalent, planar ions of the CH3+ type carbonium ions.
general concept of hydrocarbon cations, including the If the name is considered analogous to other onium ions
realization that five (and higher) coordinate carbocations (ammonium, sulfonium, phosphonium ions), then it
are the key to electrophilic reactions at single bonds in should relate to the higher-valency or coordination-state
saturated hydrocarbons (alkanes, cycloalkanes). In 1972, carbocations. These, however, clearly are not the tri-
I offered a general definition of carbocations based on the valent, but the penta- or higher-coordinated, cations of
realization that two distinct classes of carbocations
the CH5+ type. The earlier German and French literature,
exist.40 I also suggested naming the cations of carbon
indeed, frequently used the “carbenium ion” naming for
compounds “carbocations” (because the corresponding
trivalent cations.
anions were named “carbanions”).40 To my surprise, the
name stuck and was later officially adopted by the Trivalent carbenium, ions are the key intermediates
International Union of Pure and Applied Chemistry for in electrophilic reactions of π-donor unsaturated hydro-
general use.41 carbons. At the same time, pentacoordinated carbonium
ions are the key to electrophilic reactions of σ-donor
Trivalent (“classical”) carbenium ions contain an sp2-
saturated hydrocarbons through the ability of C-H or
hybridized electron-deficient carbon atom, which tends
to be planar in the absence of constraining skeletal C-C single bonds to participate in carbonium ion forma-
rigidity or steric interference. The carbenium carbon tion.
contains six valence electrons; thus it is highly electron Some characteristic bonding natures in typical non-
deficient. The structure of trivalent carbocations can classical ions are the following:
always be adequately described by using only two-
electron two-center bonds (Lewis valence bond struc-
tures). CH3+ is the parent for trivalent ions.
Pentacoordinate (or higher) (“nonclassical”) carbonium
ions contain five or (higher) coordinate carbon atoms.
They cannot be described by two-electron two-center
single bonds alone but also necessitate the use of two-
electron three (or multi)-center bonding. The carbocation

(39) Olah, G. A.; Prakash, G. K. S.; Williams, R. E.; Field, L. D.;

Wade, K. Hypercarbon Chemistry; Wiley: New York, 1987.
(40) Olah, G. A. J. Am. Chem. Soc. 1972, 94, 808.
(41) Compendium of Chemical Terminology: IUPAC Recommenda-
tions; Blackwell Scientific Publication: Oxford, 1987.
Perspective J. Org. Chem., Vol. 66, No. 18, 2001 5953

Expansion of the carbon octet via 3d orbital participa- bonding (Lewis bond), which Langmuir further devel-
tion is not possible; there can be only eight valence oped. It was Linus Pauling, and others following him,
electrons in the outer shell of carbon, a small first-row who subsequently applied the principles of the developing
element. The valency of carbon therefore cannot exceed quantum theory to the questions of chemical bonding. I
four. Kekulé’s concept of the tetravalence of carbon in prefer to use “chemical bonding” instead of “chemical
bonding terms represents attachment of four atoms (or bond,” because, after all, in a strict sense the chemists’
groups) involving 2e-2c Lewis-type bonding. However, beloved electron pairs do not exist. Electrons move
nothing prevents carbon from also participating in mul- individually, and it is only the probability that they are
ticenter bonding involving 2e-3c (or multicenter) bonds. found paired in close proximity that justifies the practical
In the 1930s, Pauling still believed that diborane had term of covalent electron-pair bonding. Pauling showed
an ethane like structure and suggested this to Kharasch that electron pairs occupying properly oriented orbitals
during a visit to Chicago (as recalled by H. C. Brown). It (which are their preferred locations, but do not exist
was Lipscomb, Pauling’s student, who in the 1950s otherwise) result in the tetrahedral structure of methane
introduced the two-electron three-center (2e-3c) bonding (involving sp3 hybridization). However, neither Lewis,
concept into boron chemistry, while also explaining the Langmuir, nor Pauling considered that an already shared
bridged structure of diborane. electron pair could further bind an additional atom, not
It is remarkable that chemists long resisted making just two. It was Lipscomb who revolutionalized the
the connection between boron and electron deficient bonding nature of boron chemistry by introducing the
carbon, which, after all, are analogues. I was lucky to be concept of two electron three or multi center bonding. It
given the opportunity to be able to establish the general was my good fortune that I was able to generalize a
concept of five and higher coordination of electron- related concept to higher coordinate carbon compounds
deficient carbon and thus be able to open up the field of and their chemistry.
hypercarbon chemistry. Whereas the differentiation of limiting trivalent and
Organic chemists who are dealing with carbon com- penta- or higher coordinate carbocations serves a useful
pounds (or perhaps more correctly with hydrocarbons and purpose in establishing the significant differences be-
their derivatives) have long considered that 2e-3c bond- tween these ions, it must be emphasized that these
ing was limited to some “inorganic” or at best “organo- represent only the extremes of a continuum and that
metallic” systems and to have no relevance to their field. there exists a continuum of charge delocalization com-
The long-drawn-out and sometimes highly personal prising both intra- and intermolecular interactions. This
nonclassical ion controversy was accordingly limited to can involve participation of neighboring n-donor atoms,
the structural aspects of some, to most chemists rather π-donor groups or σ-donor C-H or C-C bonds.
obscure, carbocations. Herbert Brown, one of the major Neighboring group participation (a term introduced by
participants in the debate and, besides Lipscomb, one of Winstein) with the vacant p-orbital of a carbenium ion
the great boron chemists of our time, was steadfast in center contributes to its stabilization via delocalization,
his crusade against bridged nonclassical ions. He repeat- which can involve atoms with unshared electron pairs
edly used the argument that if such ions existed, a new, (n-donors), π-electron systems (direct conjugate or allylic
yet unknown bonding concept would need to be discov- stabilization), bent σ-bonds (as in cyclopropylcarbinyl
ered to explain them. This, however, is certainly not the cations), and C-H and C-C σ-bonds (hyperconjugation).
case. The close relationship of electron-deficient carbo-
Hyperconjugation is the overlap interaction of an
cations with their neutral boron analogues has been
appropriately oriented σ-bond with a carbocationic F-
frequently pointed out and discussed starting with my
orbital to provide electron delocalization with minimal
1971 paper with DeMember and Commeyras. In it, we
accompanying nuclear reorganization. Nuclear reorgani-
pointed out the observed close spectral (IR and Raman)
zation accompanying σ-bond delocalization can range
similarities between isoelectronic +C(CH3)3 and B(CH3)3
from little or no rearrangement (hyperconjugation) to
and emphasized the point repeatedly thereafter. My
partial bridging involving some reorganization of nuclei
colleagues Robert Williams, Surya Prakash, and Leslie
(σ-participation) and to more extensive or complete
Field did a fine job in carrying the carbocation, borane,
bridging. Trivalent carbenium ions, with the exception
and polyborane analogy much further, and we also
of the parent CH3+, consequently always show varying
reviewed the topic in depth in our book, Hypercarbon
degrees of delocalization. Eventually in the limiting case
Chemistry.
carbocations become pentacoordinated carbonium ions.
One of the cornerstones of the chemistry of carbon com- The limiting cases define the extremes of the spectrum
pounds (organic chemistry) is Kekulé’s concept, proposed of carbocations.
in 1858, of the tetravalence of carbon. Although it was
independently also proposed in the same year by Couper,
he however, got little recognition for it. It is generally
attributed to Kekulé that carbon can bind at the same
time to not more than four other atoms or groups.
Kekulé’s tetravalent carbon was explained later on this
basis of the atomic concept and the “rule of eight” valence
electrons. From this, G. N. Lewis introduced the electron-
pair concept and that of covalent shared electron-pair

(42) For reviews comparison and references, see: Electron Deficient Under superacidic, low nucleophilicity so-called “stable
Boron and Carbon Chemistry; Olah, G. A., Wade, K., Williams, R. E.,
Eds.; Wiley-Interscience: New York, 1991. ion conditions,” developing electron-deficient carbocations
(43) Winstein, S.; Trifan, D. J. Am. Chem. Soc. 1952, 74, 1154. do not find reactive external nucleophiles to react with;
5954 J. Org. Chem., Vol. 66, No. 18, 2001 Perspective

thus, they stay persistent in solution stabilized by tures.50,51 The monopositively charged trigonal bipyr-
internal neighboring group interactions. amidal50 {[(C6H5)3PAu]5C}+ and the dipositively charged
octahedral52 gold complex {[(C6H5)3PAu]6C}2+ contain
8. Five and Higher Coordinate Carbocations and five- and six-coordinate carbon, respectively. Considering
Their Chemistry the isolobal relationship (i.e., similarity in bonding)
between LAu+ and H+, the gold complexes represent the
On the basis of my extensive study of stable, persistent isolobal analogues of CH5+ and CH62+.
carbocations, reported in more than 300 publications, as
mentioned I was able in 1972 to develop a general concept
of carbocations.40 In higher-coordinate (hypercoordinate)
carbonium ions, of which protonated methane CH5+ is
the parent, besides two-electron two-center Lewis bond-
ing, two-electron three-center bonding is involved.
Extensive ab initio calculations44 reconfirmed the
preferred Cs symmetrical structure for the CH5+ cation,
as we originally suggested with Klopman in 1969.45 The The remarkable stability of the gold complexes is due
structure can be viewed as a proton inserted into one of to significant metal-metal bonding. However, their
the σ C-H bonds of methane to form a 2e-3c bond isolation and structural study are remarkable and greatly
between carbon and two hydrogen atoms (or CH3+ contributed to our knowledge of higher-coordinate car-
binding H2 through a long, weaker bonding interaction). bocations.
At the same time, we already pointed out with Klopman Boron and carbon are consecutive first-row elements.
that ready bond-to-bond (isotopal) proton migration can Trivalent carbocations are isoelectronic with the corre-
take place through low barriers to equivalent or related sponding neutral trivalent boron compounds. Similarly,
structures that are energetically only slightly less favor- pentavalent monopositively charged carbonium ions are
able (which led more recently to Schleyer’s suggestion of isoelectronic with the corresponding neutral pentavalent
a fluxional, completely delocalized nature).46 boron compounds. BH5, which is isoelectronic with CH5+,
In 1982, we studied the parent six-coordinate dipro- has also a Cs symmetrical structure based on high-level
tonated methane (CH62+),47 which has two 2e-3c bonding ab initio calculations.52,53 Experimentally, H-D exchange
interactions in its minimum-energy structure (C2v).48 On was observed in our work when BH4- was treated with
the basis of ab initio calculations, with Rasul we more deuterated strong acids, indicating the intermediacy of
recently found that the seven-coordinate triprotonated isotopomeric BH5.54 The first direct experimental obser-
methane (CH73+) is also an energy minimum and has vation (by infrared spectroscopy) of BH5 has only recently
three 2e-3c bonding interactions in its minimum-energy been reported.55 The X-ray structure of the five-coordinate
structure (C3v). These results further indicate the general gold complex [(Cy3P+)B(AuPPh3)4] was also reported by
importance of 2e-3c bonding in protonated alkanes. Schmidbaur.56 This square-pyramidal compound repre-
sents the isolobal analogue of BH5 and further strength-
ens the relationship of the bonding nature of higher-
coordinate boron and carbon compounds.
As five- and six-coordinate CH5+ and CH62+ are iso-
electronic with BH5 and BH6+,57 respectively, seven-
coordinate tripositively charged CH73+ 48 is isoelectronic
with the corresponding dipositively charged heptavalent
boronium dication BH72+.57 We have also searched for a
Protonated methanes and their homologues and de- minimum-energy structure of tetraprotonated methane,
rivatives are experimentally indicated in superacidic CH84+. However, CH84+ remains even computationally
chemistry by hydrogen-deuterium exchange experi- elusive because charge-charge repulsion appears to have
ments, as well as by core electron (ESCA) spectroscopy reached its prohibitive limit. The isoelectronic boron
of their frozen matrixes.49 Some of their derivatives could analogue BH83+, however, was calculated to be an energy
even be isolated as crystalline compounds. In recent minimum.57
years, Schmidbaur has prepared gold complex analogues The discovery of a significant number of hypercoordi-
of CH5+ and CH62+ and determined their X-ray struc- nate carbocations (“nonclassical” ions), initially based on
solvolytic studies and subsequently as observable, stable
(44) (a) Raghavachari, K.; Whitesides, R. A.; Pople, J. A.; Schleyer,
P. v. R. J. Am. Chem. Soc. 1981, 104, 3258. (b) Dyczmons, V.;
ions in superacidic media as well as on theoretical
Staemmler, V.; Kutzelnig, W. Chem. Phys. Lett. 1970, 5, 361. (c) calculations, showed that carbon hypercoordination is a
Lathan, W. A.; Hehre, W. J.; Pople, J. A. Tetrahedron Lett. 1970, 2699. general phenomenon in electron-deficient hydrocarbon
(d) Lathan, W. A.; Hehre, W. J.; Pople, J. A. J. Am. Chem. Soc. 1971,
93, 808.
(45) Olah, G. A.; Klopman, G.; Schlosberg, R. H. J. Am. Chem. Soc. (50) Scherbaum, F.; Grohmann, G.; Müller, G.; Schmidbaur, H.
1969, 91, 3261. Angew. Chem., Int. Ed. Engl. 1989, 28, 463.
(46) (a) Schreiner, P. R.; Jim, S.-J.; H. f. Schaefer, Schleyer, P. v. R. (51) Scherbaum, F.; Grohmann, G.; Huber, B.; Krüger, C.; Schmid-
J. Chem. Phys. 1993, 99, 3716. (b) Scuseria, G. E. Nature 1993, 366, baur, H. Angew. Chem., Int. Ed. Engl. 1988, 27, 1544.
512. (52) Schreiner, P. R.; Schaefer, H. F.; Schleyer, P. v. R. J. Chem.
(47) (a) Lammertsma, K.; Olah, G. A.; Barzaghi, M.; Simonetta, M. Phys. 1994, 101, 7625.
J. Am. Chem. Soc. 1982, 104, 6851. (b) Lammertsma, K.; Barzaghi, (53) Watts, J. D.; Bartlett, R. J. J. Am. Chem. Soc. 1995, 117, 825.
M.; Olah, G. A.; Pople, J. A.; Schleyer, P. v. R.; Simonetta, M. J. Am. (54) Olah, G. A.; Westerman, P. W.; Mo, Y. K.; Klopman, G. J. Am.
Chem. Soc. 1983, 105, 5268. Chem. Soc. 1972, 94, 7859.
(48) Olah, G. A.; Rasul, G. J. Am. Chem. Soc. 1996, 118, 8503. (55) Tague, T. J.; Andrews, L. J. Am. Chem. Soc. 1994, 116, 4970.
(49) Olah, G. A.; Prakash, G. K. S.; Williams, R. E.; Field, L. D.; (56) Blumenthal, A.; Beruda, H.; Schmidbaur, H. J. Chem. Soc.,
Wade, K. Hypercarbon Chemistry; John Wiley & Sons: New York, 1987; Chem. Commun. 1993, 1005.
p 149. (57) Rasul, G.; Olah, G. A. Inorg. Chem. 1997, 36, 1278.
Perspective J. Org. Chem., Vol. 66, No. 18, 2001 5955

systems. Some characteristic nonclassical carbocations hypercarbon compounds, including alkyl (acyl)-bridged
are the following. organometallics as well as carboranes, carbonyl, and
carbide clusters, are now recognized and have been
studied. They are reviewed in our book Hypercarbon
Chemistry (written with Prakash, Williams, Field, and
Wade).49
During my studies related to the nonclassical ion
problem, I realized that the formation of the σ-delocalized
2-norbornyl cation from 2-norbornyl precursors repre-
sented the equivalent of an intramolecular σ-alkylation
where a covalent C1-C6 bond provided the electrons for
the 2e-3c bonded bridged ion (by σ-participation).60

The formation of the σ-delocalized norbornyl cation via

ionization of 2-norbornyl precursors in low-nucleophilic-
ity, superacidic media can be considered an analogue of
an intramolecular Friedel-Crafts alkylation in a satu-
rated system. Indeed, deprotonation gives nortricyclane.60

According to early theoretical calculations which Klop-

man and I carried58 out in 1971, the parent molecular
ions of alkanes, such as CH4+, observed in mass spec- The intramolecular σ-delocalization in the norbornyl
trometry, also can have a planar hypercarbon structure, system aroused my interest in studying whether similar
although distortion is probable. electrophilic interactions and reactions of C-H or C-C
bonds are possible in intermolecular systems. This led
to the discovery of the general electrophilic reactivity of
saturated hydrocarbons and single bonds in general.
The long, drawn-out nonclassical ion controversy thus
led to an unexpected new chapter of chemistry. As
The CH42+ ion, as calculated later by Radom, however frequently happens in science, the drive for understand-
has a completely planar C2v structure.59 ing (for whatever reason) of what appear at the time to
Not only can carbon be involved in a single two-electron be rather isolated and even relatively unimportant
three-center bond formation, but also some carbodications problems can eventually lead to significant new concepts,
simultaneously participate in two 2e-3c bonds. Diproton- new chemistry, and even practical applications. It justi-
ated methane (CH62+)47 and ethane (C2H82+),47 as well as fies the need for exploration and study in the context of
the dimer of the methyl cation (C2H62+),47 are illustrative. fundamental (basic) research even if initially no practical
reasons or uses are indicated. The beauty of science lies
in finding the unexpected, but as Niels Bohr was fre-
quently quoted to have said, “you must be prepared for
a surprise”. At the same time, you must also understand
what your findings mean and what they can be used for.
To me, this is the lesson of the norbornyl ion controversy.
I believe it was not a waste of effort to pursue it, and
eventually it greatly helped to advance chemistry to new
It was the study of hypercarbon-containing nonclassical
areas of significance that are still emerging.
carbocations that allowed us to firmly establish carbon’s
To illustrate the significance of higher coordinate
ability in a hydrocarbon system to bind simultaneously
carbocations in hydrocarbon chemistry61 some examples
with five (or six or even seven) atoms or groups. It should
are illustrative.
be emphasized that carbocations represent only one class
of hypercarbon compounds. A wide variety of neutral
(60) Olah, G. A.; Prakash, G. K. S.; Saunders, M. Acc. Chem. Res.
1983, 16, 440.
(58) Olah, G. A.; Klopman, G. Chem. Phys. Lett. 1971, 11, 604. (61) Olah, G. A.; Molnar, A. Hydrocarbon Chemistry; Wiley: New
(59) Wong, M. W.; Radom, L. J. Am. Chem. Soc. 1989, 111, 1155. York 1995 and references therein.
5956 J. Org. Chem., Vol. 66, No. 18, 2001 Perspective

Protonation (and protolysis) of alkanes is readily nature of zeolite catalysts was also successfully explored
achieved with superacids. The protonation of methane in cases such as H-ZSM-5 at high temperatures.63
itself to CH5+, as discussed earlier, takes place readily. Not only protolytic reactions but also a broad range of
reactions with varied electrophiles (alkylation, formyl-
ation, nitration, halogenation, oxygenation, etc.) were
found to be feasible when using superacidic, low-nucleo-
philicity reaction conditions.61,64

Acid-catalyzed isomerization reactions of alkanes as

well as their alkylation and condensation reactions are
initiated by protolytic ionization. Available evidence
indicates nonlinear but somewhat bent, although not
triangular transition states.62

Alkylation of isoalkanes with alkenes is of particular

significance. The industrially used alkylation of isobutane
The reverse reaction of the protolytic ionization of with isobutylene to isooctane, is, however, de facto
hydrocarbons to carbocations, that is, the reaction of alkylation of the reactive isobutylene and not of the
trivalent carbocations with molecular hydrogen giving saturated hydrocarbon. Isobutane only acts as a hydride
their parent hydrocarbons, involves the same five- transfer agent and a source of the tert-butyl cation,
coordinate carbonium ions. formed via intermolecular hydride transfer. In contrast,
when the tert-butyl cation is reacted with isobutane
under superacidic conditions and thus in the absence of
isobutylene, the major fast reaction is still hydride
transfer, but a detectable amount of 2,2,3,3-tetra-
methylbutane, the σ-alkylation product, is also obtained.
The isomerization of butane to isobutane in superacids With sterically less crowded systems σ-alkylation be-
is illustrative of a protolytic isomerization, where no comes more predominant.61
intermediate olefins are present in equilibrium with
carbocations.
The superacid-catalyzed cracking of hydrocarbons (a
significant practical application) involves not only forma-
tion of trivalent carbocationic sites leading to subsequent
â-cleavage but also direct C-C bond protolysis.

A fundamental difference exists between conventional

acid- and superacid-catalyzed hydrocarbon chemistry. In
the former, trivalent carbenium ions are always in
equilibrium with olefins, which play the key role, whereas
in the latter, hydrocarbon transformation can take place
without the involvement of olefins through the interme-
diacy of five-coordinate carbocations.61
The reaction of trivalent carbocations with carbon
Whereas superacid (HF/BF3, HF/SbF5, HF/TaF5, FSO3H/
monoxide giving acyl cations is the key step in the well-
SbF5, etc.) catalyzed hydrocarbon transformations were
known and industrially used Koch-Haaf reaction of
first explored in the liquid phase, subsequently, solid acid
preparing branched carboxylic acids from alkenes or
catalyst systems, such as those based on Nafion-H,
alcohols. For example, in this way, isobutylene or tert-
longer-chain perfluorinated alkanesulfonic acids, fluori-
butyl alcohol is converted into pivalic acid. In contrast,
nated graphite intercalates, etc. were also developed and
utilized for heterogeneous reactions. The strong acidic
(63) Haag, W. O.; Dessau, R. H. Int. Catal. Congr. Proc. 8th 1984,
II, 105.
(62) Olah, G. A.; Klopman, G.; Schlosberg, R. H. J. Am. Chem. Soc. (64) Olah, G. A.; Prakash, G. K. S.; Mathew, T.; Marinez, E. R.
1969, 91, 3261. Angew. Chem., Int. Ed. 2000, 2647.
Perspective J. Org. Chem., Vol. 66, No. 18, 2001 5957

based on the superacidic activation of electrophiles are not unique to alkane activation processes. The C-H
leading to superelectrophiles we found it possible to (and C-C) bond activation by organometallic complexes,
formylate isoalkanes to aldehydes, which subsequently such as Bergman’s iridium complexes and other transi-
rearrange to their corresponding branched ketones.64 tion metal systems (rhodium, osmium, rhenium, etc.), is
These are effective high-octane gasoline additive oxygen- based on somewhat similar electrophilic insertions. These
ates. The conversion of isobutane into isopropyl, methyl reactions, however, cannot as yet be made catalytic,
ketone, or isopentane into isobutyl, methyl ketone is although future work may change this. A wide variety
illustrative. In this reaction, no branched carboxylic acids of further reactions of hydrocarbons with coordinatively
(Koch products) are formed. unsaturated metal compounds and reagents involving
hypercarbon intermediates (transition states) is also
recognized, ranging from hydrometalations to Ziegler-
Natta polymerization.61
In the conclusion of my 1972 paper40 on the general
concept of carbocations I wrote, “The realization of the
electron donor ability of shared (bonding) electron pairs
of single bonds, should rank one day equal in importance
The superacid-catalyzed electrophilic oxygenation of with that of unshared (nonbonding) electron pairs rec-
saturated hydrocarbons, including methane with hydro- ognized by Lewis. We can now not only explain the
gen peroxide (via H3O2+) or ozone (via HO3+), allows the reactivity of saturated hydrocarbons and in general of
efficient preparation of oxygenated derivatives.65 single bonds in electrophilic reactions, but indeed use this
understanding to explore new areas of carbocation chem-
istry”.
This was one of the few times I ever made a prediction
of the possible future significance of my chemistry. More
than a quarter of a century later, I take some satisfaction
that I was correct and that, indeed, hypercarbon chem-
istry has a significant place on the wide palette of
chemistry.
Carbon can extend its bonding from Kekulé’s66 tetra-
valent limit to five-, and even higher-bonded (coordinate),
hypercarbon systems. Higher coordinate carbocations are
now well recognized. They are the key to our understand-
ing of the electrophilic reactivity of C-H or C-C single
bonds and of hypercarbon chemistry in general. Some of
their derivatives, such as related gold complexes, can
even be isolated as stable crystalline compounds. The
chemistry of higher-coordinate carbon (i.e., hypercarbon
chemistry) is rapidly expanding, with many new vistas
to be explored. The road from Kekulé’s tetravalent carbon
Because the protonation of ozone removes its dipolar to hypercarbon chemistry took more than a century to
nature, the electrophilic chemistry of HO3+, a very travel. Carbon also unveiled other unexpected new
efficient oxygenating electrophile, has no relevance to aspects, for example, its recently discovered fullerene-
conventional ozone chemistry. The superacid-catalyzed type allotropes and their chemistry. There is no reason
reaction of isobutane with ozone giving acetone and to believe that the new century just beginning will not
methyl alcohol, the aliphatic equivalent of the industri- bring much further progress in the fascinating field of
ally significant Hock reaction of cumene, is illustrative. hypercarbon chemistry, to which knowledge of carbo-
cations made essential contribution.

Acknowledgment. My work on carbocations would

have not been possible without the fundamental con-
tributions and hard work of my dedicated students,
collaborators, and colleagues I was privileged to work
with over the years. They became an integral part of
the Olah group and my broader scientific family, many
personal friends as well. Their names are to be found
in the literature citations and my recently published
autobiography.1 I would like, however, to specifically
thank Professor G. K. Surya Prakash who started with
me a quarter century ago as a graduate student and
continues as my colleague and close friend in our still
continuing cooperation in search for the wonderful
Electrophilic insertion reactions into C-H (and C-C) challenges of carbocation chemistry.
bonds under low-nucleophilicity superacidic conditions
JO010438X
(65) Olah, G. A.; Yoneda, N.; Parker, D. G. J. Am. Chem. Soc. 1976, (66) Kekulé, G. A. Ann. 1858, 106, 129. Kekulé, F. A. Z. Chem. 1867,
98, 5261. 3, 217.