Chemistry of Carbocations

3.1 BACKGROUND [1-47]

The conversions of hydrocarbons promoted by acid catalysts involve more or less short-lived
cationic reaction intermediates known as carbocations. The chemistry of carbocations, the
sophisticated foundation of knowledge developed progressively during the 20thcentury, pro-
vides an excellent means of rationalising these conversions. This chemistry hinges around
two types of carbocation: the carbenium ion R,C+, which has been known for a considerable
period of time, and the carbonium ion R,C+, been discovered much more recently.
Although the concept of carbocation R3Cf is generally attributed to von Baeyer and Villiger
(1902) [8], it was in fact probably devised by Stieglich, dating back to the end of the 19* cen-
tury [9]. The cationic nature of some organic compounds, such as the triarylmethyl salts, was
known and accepted at the start of the 20th century, but due to the non-ionic nature of most
hydrocarbons and the difficulty of activating them electrochemically, scientists had long
rejected the idea that a hydrocarbon could, during a reaction, split into two fragments, one car-
rying a positive charge and the other a negative charge. Consequently, this idea only devel-
oped very slowly. It was not until the start of the 1920's that the concept of cationic reaction
intermediatewas revived by Meenvein [3a, 101 during his work on the Wagner rearrangement
of camphene in liquid phase. In the 1930's, several scientists working on organic reactions
played a major role in raising support for this concept. Whitmore in particular is one of the
key figures, possibly the greatest, responsible for generalising the carbocationic concept [ 1 1,
121: in 1932, he proposed the intervention of the carbenium ion as reaction intermediate in the
polymerisation of olefins and the alkylation of aromatics by the olefins [ 1I], later suggesting
their probable intervention in the catalytic cracking reaction [12]. He also proposed the 1,2
shift to explain some rearrangements [3b]. In 1934, he asserted that the acid sites are the active
centres responsible for the formation of carbocations [ 131, an idea which was not immediately
accepted by the scientific community. Other famous scientists [3b] also made important con-
tributions before the middle of the 20th century: Bartlett [3b, 141, Wilson, Winstein, Cram,
Dewar, Roberts, Schleyer, etc. In 1944, for example, Bartlett demonstrated hydride transfer
between a hydrocarbon and a carbocation [3b] in the presence of a strong liquid acid.
132 Chapter 3 Chemistry oJCarbocafions

Only carbenium ions were known at this time, and they were called “carbonium” ions. At
the end of the 194O’s, several teams of scientists, referring to the work and suggestions of
Whitmore, embarked on the rationalisation of the reactions involved in catalytic cracking on
the basis of “carbonium” ions (the current carbenium ions ) [ 151. The names of some of the
scientists in these teams are still known to this day: Hansford [ 16, 171, Greensfelder [ 18-21],
Voge and Good [ 18, 201, Thomas [22,23], Bremner [24], Ciapetta et al. [25]. In particular,
Hansford, in 1947, was the first to propose a cracking mechanism based on the carbonium
ions [16, 261. Around 1950, the hydride transfer and hydrogen transfer reactions were
demonstrated on solid catalysts by the teams of Greensfelder [18], Thomas [22] and
Hansford [ 16,271. In the early 1950’s,the protonation of unsaturated hydrocarbons (olefins,
triphenylethylene, polyaromatics) proposed by Whitmore during his studies on the olefins,
was demonstrated experimentally by UV spectroscopy in a pure sulphuric acid medium [28,
291. At the same time, numerous studies helped to identify the acid nature of solid catalysts
[22,30-361, acting either as proton donor or as highly polar Lewis acid in various reactions,
such as H2-D2 exchange, isomerisation of paraffins and cracking. Thomas [22] attributed
the acidity of silica-aluminas to the presence of trivalent aluminium in tetrahedral position
in the solid.
Towards 1950, the carbocations, regarded as species which could not be observed since
unstable and short-lived, were still considered as hypothetical species. They were neverthe-
less extremely useful since they could be used to explain numerous kinetic and stereochem-
ical studies on substitution or nucleophilic elimination reactions catalysed by acids. Olah’s
studies, carried out during the 1950’s and 1960’swith superacid media, led to the preparation
of persistent carbocations (“the qualifier “stable”, although not generally recommended [37],
will often be used later). Due to their long lifetime, direct observation and even titration
became possible on these species [3a]. The concept of carbocation had become a reality.
A scientist of Hungarian origin, Olah emigrated to Canada after the 1956 Hungarian rev-
olution and was hired by Dow Chemical Company Research Laboratory at Sarnia (Ontario).
He managed to prepare and characterise using NMR the first carbocation with a long life-
time in highly acidic medium: the tertiobutyl ion (ter-butyl ion). The presentation of his
results in 1962, at the Brookhaven conference on mechanisms, was received with very little
enthusiasm [3a]. Later studies, however, were to confirm this result and a wide range of “sta-
ble” carbocations was soon to be obtained in superacid medium [3a, 3b]. The boom in the
number of studies carried out on carbocations in the second half of the 20thcentury is largely
due to Olah, 1994 Nobel prize-winner [4] (who dedicated most of his scientific career to
them) and to his numerous co-workers.
At the start of the 1960’s, scientists were puzzled by the formulation proposed for a cer-
tain number of carbocations, including the famous 2-norbornyl cation, which displayed a
bridged “non-classical” structure. This problem was not really new, having already been
raised back in 1927 by Freudenberg [38]. Compared with the “classical” carbocations,
whose positive charge is attributed to a tricoordinated carbon, the difference with the non-
classical ions is the existence, in their formulation, of pentacoordinated carbons beside nor-
mally tetracoordinated carbons. This problem was one of the main topics of discussion in the
conferences and congresses held at the time and several publications were in fact later ded-
icated to non-classical carbocations [39,40]. Towards the end of the 19603, Olah et al. [41-
 Chapter 3 Chemistry of Carbocations 133

451 as well as Brouwer and Hogeveen [46] demonstrated the scission of a oC-C bond in a
superacid. Olah suggested that the protonation of this bond involves the intermediate for-
mation of a highly unstable structure with 3 centres (1 H and 2 C) and 2 electrons, a hyper-
coordinated structure which belongs to the category of non-classical carbocations. In
particular, Olah et af. [45] were the first to have proposed the formation of the CHf ion in
superacid solution.
In 1972, Olah suggested that those ions with at least one tricoordinated carbon (classical
structure) should be called carbenium ions and that those with at least one pentacoordinated
carbon (non-classical structure) should be called carbonium ions. This definition has been
recognised by the IUPAC since 1987 [47]. The carbenium ions play a key role in the elec-
trophilic reactions of x-electron donor unsaturated hydrocarbons, whereas the carbonium
ions are the preferred intermediates of electrophilic reactions of 0-electron donor saturated
hydrocarbons [3a].
In this chapter we will first give a brief description of the various carbocations (carbo-
nium and carbenium ions), then examine their genesis and stability, before finally describ-
ing the transformations they can undergo.

3.2 TYPE AND GENESIS OF CARBOCATIONS

(CARBENIUMAND CARBONIUM IONS)

3.2.1 Type of Carbocations

The best tool available for the study of carbocations is nuclear magnetic resonance (NMR)
spectroscopy which has been used by many scientists, especially Olah, for numerous organic
compounds placed in the presence of superacids. The resonance spectra of the proton of the
carbocations obtained with the strongest superacids, e.g. (CH,),C+ SbF,, demonstrate sig-
nificant shifts of the protons as compared with those obtained with weaker acids, e.g. ter-
butyl fluoride. The resonance spectra of I3C confirm that these species (carbenium ions) are
“stable” carbocations and not donor-acceptor complexes [3a].
After studying these spectra, as well as the behaviour of saturated hydrocarbons in
superacid medium, Olah identified two classes of carbocation (fig. 3.1 a and b):
- The tricoordinated carbenium ions (classical carbocations) have a central electron-
deficient carbon atom (fig. 3. la). With no special structural constraints, they have a
plane configuration and the bonds of the central carbon with the 3 neighbouring atoms
are then characterised by sp2 hybridisation (requiring 6 electrons).
- The carbonium ions (non-classical carbocations), generally unstable species, can be
described as ions where the carbon is pentacoordinated with 8 electrons in the valence
ring, by 3 simple o bonds and a “special bond” with 3 centres and 2 electrons
(fig. 3.lb) [3, 5, 48-50]. This type of bond is generally represented by diagram 1 of
figure 3.lb. It is sometimes represented differently, as indicated in diagrams 2 and 3
of figure 3.lb, comparable with the symmetry structures Cs and C2,, respectively of
the methonium ion.
134 Chapter 3 Chemistry of Carbocations

a.

Fig. 3.1
Diagrammatic representation of the carbenium CR; (a) and carbonium CHR;
(b) ions. Three different possibilities are shown for the carbonium ions (dia-
grams l , 2 and 3).

Although the presence of a bond with 3 centres and 2 electrons has been clearly demon-
strated in some cations, e.g. the norbornyl cation which will be discussed below (para-
graph 3.3.1.2.A.b), the pentacoordinated carbonium ions remain less well-known than the
carbenium ions.

3.2.2 Genesis of Carbocations

3.2.2.1 Genesis of Carbenium Ions

Carbenium ions can be generated from many hydrocarbon-containing species. Several reac-
tion categories have been proposed
- abstraction of a negatively-charged entity (e.g. hydride ion or halogen anion) from a
saturated or unsaturated molecule: abstraction of the C1- anion from ter-butyl chloride,
for example;
- addition of a proton or a carbenium ion to an unsaturated molecule;
- heterolytic scission of a larger carbenium ion;

- split of a carbonium ion: R5Cf + R,Cf + R,.

We may mention a fifth reaction category: formation of a carbenium ion by oxidation of

a hydrocarbon. It will only be mentioned briefly below since it does not really involve the
acid properties of the catalyst used.

A. Abstraction of a Negatively-Charged Entity from a Saturated or Unsaturated Molecule

a. From A/ky/ Halides B X (X = C/, E Br, r) [3a, 5 1]
In 1962 using NMR, Olah [3a] obtained and identified the ter-butyl cation, stable in solu-
tion, by dissolving ter-butyl fluoride in an excess of SbF, which behaves both as Lewis acid
and solvent (fig. 3.2).
 Chapter 3 Chemistry of Carbocations 135

CH3
I

Fig. 3.2
Formation of the ter-butyl cation by abstraction of the F- ion from
ter-butyl fluoride by SbF,.

b. Abstraction of a Hydride Ion K from a Saturated Hydrocarbon

by a Brransted Acid Side (Proton H+), with Formation of Hydrogen
For a paraffin, the reaction is written:

where S- is the conjugated base of the acid.

The mechanism of this well-known reaction [43] is a protolysis of a C-H bond of the
hydrocarbon, involving the formation of a bond with 3 centres and 2 electrons (carbonium
ion) then scission of this bond into a carbenium ion and hydrogen [44](scission of a carbo-
nium ion will be discussed in 3.4.2). The C-C bonds, however, may also undergo protolysis
with formation of a smaller carbenium ion and a paraffin according to the following reaction:

CnH2nt2 -k Hf (CnH2n+3)+ (CiH2i+l)t -k Cn-iH2(n-i)+2

As we will see below (paragraphs 3.4.2, 4.1 and chapter 11, “Catalytic cracking”), the
formation of very light hydrocarbon-containing fragments, first observed during the crack-
ing of alkanes, is at least partly explained by this mechanism.

c. Abstraction of a Hydride Ion K from a Saturated Hydrocarbon

by a Lewis Acid Side L or by a Carbonium Ion R‘
Abstraction of a hydride ion H- by a Lewis site L was soon proposed as a possibility [18,
22, 52-54]:
R-CH2-CH2-CH3 + L + R-CH+-CH2-CH3 + L-H
Unfortunately, there is no experimental proof for this hypothesis or it is based on exper-
imental arguments which are not always convincing [43, 55-62]. For example, the well-
known formation of the ter-butyl carbenium ion by placing isobutane in contact with the
Lewis acid SbF, is put down, not to a simple hydride abstraction with formation of a Sb-H
bond (which is in fact not very stable), but to an oxidation reaction [63] which will be
described below in paragraph 3.2.2.1.D.
This hypothesis is even at variance with several experimental facts. For instance, a
hydride ion can only be removed from triphenylmethane with a Brmsted acid [64]. Also,
Lewis acid solids such as AlCl, are only active during the isomerisation of alkanes in the
136 Chapter 3 Chemistry of Curbocutions

presence of a small amount of water, which generates protonic acidity, of alkenes or of alkyl
chlorides which initiate the reaction [56, 651.
In contrast, the following reaction of hydride abstraction by a carbenium ion (which is
itself a Lewis acid) is well-known and widely accepted by the scientific community [52,60,
66-72]:
R-CH2-CH2-CH, + Rf + R+CHf-CH2-CH, + R-H

d. Abstraction of a Hydride Ion K from an Olefin

Abstraction of the hydride ion can be carried out by a proton (with formation of hydrogen)
or by a carbenium ion (which in this case desorbs as a paraffin). Abstraction by a Lewis acid
site L could also be considered, but faces the same reserves as those stated above.

R-CH2-CH=CH2 + Ht + R-CHt-CH=CH2 + H,
R-CH2-CH=CH2 + R-CHfR -+ R-CH+-CH=CH, + R-CH2-R
R-CH,-CH=CH, +L + R-CH+-CH=CH, + L-H
The allylic carbocation formed is more stable than the corresponding saturated carbenium
ion.

B. Addition of a Proton or a Carbenium Ion on a Molecule with a Double or Triple Bond

a. Addition on an O/efin or an Aromatic [5 1, 601
Addition of a Proton (fig. 3.3)

R-CH=CH2 + H+ - R-CH+-CH3

cH3 CH3 xylenium ion

Fig. 3.3
Addition of a proton on an olefin and on an aromatic ring.

Addition of a Carbenium Ion

Addition of a carbenium ion on an alkene always occurs preferentially via the pathway
which leads to the carbenium ion where the charge is located on the most substituted car-
bon:
R-CH=CH2 + R" + R-CH+-CH,-R'
 Chapter 3 Chemistry of Carbocations 137

A similar reaction may occur between an aromatic ring and a carbenium ion.
These reactions, long accepted by the scientific community, are involved in numerous
hydrocarbon conversions which will be discussed below.

b. Addition of a Proton on Acetylene [3fl

Addition of a proton to acetylene results in the formation of a vinyl carbocation, for which
calculations show that the most probable structure is that where the proton is in bridged posi-
tion between the two carbons (fig. 3.4).

H+
C H e C H + H+ - **# . ,,
CH-CH

Fig. 3.4
Addition of a proton on an acetylene. Bridged structure of the vinyl carboca-
tion obtained from acetylene.

If the vinyl carbocation is substituted (CRSR'), calculations show that it then prefers to
adopt an open structure where the C+-R' bond is colinear with the double bond [3fl:
C R S R ' + H+ + CHR=C+-R'

C. Scission of a Carbenium ion, Alkyiation by a Carbenium ion and Split of a Carbonium ion
We will see below (paragraph 3.4.1.1.B)that the scission of a carbenium ion occurs het-
erolytically on the p bond with respect to the positively charged carbon. This reaction, which
results in the formation of a smaller carbenium ion and an olefin, can be written:
(CnH*n+l)++ (CmH2m+l)++ C n-mH2(n-m)
The alkylation reaction of a carbenium ion on an olefin is the reverse reaction.
Scission of a carbonium ion has already been mentioned (paragraph 3.2.2.1.A): it results
in the formation of a smaller carbenium ion and a paraffin.

D. Formationof a Carbenium ion by an Oxido-ReductionReaction

The accepted mechanism for the formation of the ter-butyl carbenium ion, by reaction
between isobutane and the superacid HF-SbF,, is that seen in the previous paragraph: pro-
tonic attack of the C-H bond of the tertiary carbon forms the short-lived tertiobutonium ion
(carbonium ion), which then rapidly splits into a ter-butyl carbenium ion and hydrogen.
Globally, the reaction can be summarised as hydrogen abstraction from isobutane according
to a purely acid mechanism [60,63,73-75].
The magic acid HFS0,-SbF, placed in contact with isobutane forms the ter-butyl ion
faster than the superacid HF-SbF,, even though the latter is stronger, whilst producing less
138 Chapter 3 Chemistry of Carbocations

hydrogen than expected. With magic acid, it appears that, at the same time as the hydrogen
abstraction described previously, there is also an oxidation reaction by the Lewis acid SbF,
which could include the following steps [63]:
2RH + 2SbF5 + 2RtSbF,H-
SbFSH- + 2SbF5 + SbF, + SbF3 + HSbF,
SbFSH- + HSbF, + SbF, + H2 + SbF,
i.e. a total of: 2RH + 3SbF5 + 2RfSbF, + SbF, + H,
However, with the acid HF-SbF,, the hydride abstraction is mainly due to the proton and
one hydrogen molecule is produced for each hydrocarbon molecule.
This type of oxidation reaction has been confirmed by other authors for SbF, alone [76,
771 as well as for H2S04[51,76,78]. Conversion of the alkane into carbenium ion, with the
creation of an intermediate radical or radical ion, has also been proposed [60, 76, 79-81],
especially for sulphated zirconia, but this pathway still remains to be confirmed.

3.2.2.2 Genesis of Carboniurn Ions

The carbonium ion can be produced by various types of electrophilic attack.

A. Attack of a oC-H Bond by a Proton [44]

to Form the Bond with 3 Centres and 2 Electrons 1C2H
This bond is shown on figure 3.5a. Observations in superacid medium and molecular orbital
calculations carried out on the simplest carbonium ion, the methonium ion CHf, indicate
that it could take several different configurations, but with similar energies, which would
exist in dynamic equilibrium [67].

B. Attack of the Hydrogen Molecule by a Carbenium Ion

to Form the Bond with 3 Centres and 2 Electrons 1C2H
Addition in gaseous phase of hydrogen to the ethyl carbenium ion C2Hf results, under
-130"C, with no energy barrier, in the formation of the ethonium ion C,H$, characterised by
the previous bond 1C2H [82] and which can be considered as an ethane molecule protonated
on one of the two carbons.

C. Attack of a oC-C Bond by a Proton [44]

to Form the Bond with 3 Centres and 2 Electrons 2ClH
The 2C 1H type bond with 3 centres and 2 electrons, formed by addition of a proton on a
o C - C bond, is shown on figure 3.5b.
Formally, the 2C1H bond also forms by reaction between a carbocation and a C-H bond,
the reaction occurring more easily the more electrophilic the Lewis acid carbocation. This
bond forms briefly in the hydride transfer reaction, discussed previously in para-
graph 3.2.2.1.A.c. It also probably forms in the alkylation reaction by ethylene of methane
at 50°C or of ethane on the superacid catalyst HF-TaF,: protonation of ethylene would result
 Chapter 3 Chemistry of Carbocations I39

in the highly reactive ethyl primary carbocation, which would then attack the C-H bond of
the methane or the ethane to form respectively propane and n-butane [45,48, 82, 831.
The 2C1H type bond with 3 centres and 2 electrons can also be obtained by isomerisa-
tion of a carbonium ion initially including a 1C2H bond. This is the case, for example, of
the ethonium ion, which is produced with a 1C2H type bond with 3 centres and 2 electrons
by addition of hydrogen to the ethyl ion below -130°C, but rearranges between -100 and
40°C, with a small energy barrier, into the more stable ethonium ion characterised by a
2CIH bond [84]. In the latter case, the ethonium ion can be considered as a molecule of
ethane protonated on the C-C edge.

D. Attack of a o C - C Bond by a Carbenium Ion

to Form the 3C Type Hypothetical Bond with 3 Centres and 2 Electrons
Formation of the 3C type bond shown on figure 3.5c, where the 3 centres are carbons, was
envisaged by Olah [85] and Hogeveen [86]. It is a priori very difficult and, as far as we
know, has not yet been identified [86, 871 at the normal temperatures at which liquid
superacids are used. Formation of such an intermediate carbonium ion probably requires, in
fact, an extremely strong Lewis acid carbocation.
Generally, in view of their low basicity, the oC-H and oC-C bonds can only be attacked,
at ambient or below ambient temperature, by very strong acids or electrophiles (superacids).
This is probably why the only examples identified here concern activation of the C-H bond
by a proton or a primary carbenium ion, as well as activation of the H-H bond by a carbe-
nium ion or activation of the C-C bond by a proton.

E. Comment on the Genesis of Carbonium Ions

If we restrict ourselves to the attack of oC-H and oC-C bonds by proton, three structures can
be considered: the first is the 1C2H type shown on figure 3.5a, the second is the 2C1H non-
linear bridged structure on figure 3.5b and the third is a 2C1H linear bridged structure (H
between the 2 carbons), which is an isomer of the previous one [63,67,88]. For a hydrocar-
bon with n carbons, these three structures must be considered for each secondary carbon [67].

a. b. C.
I

Fig. 3.5
Formation of a carbonium ion by electrophilic attack of a CJ bond by a posi-
tively charged centre (proton or carbenium ion) with formation of a bond with
3 centres and 2 electrons of type 1C2H (a), 2C1H (b), 3C (c).
140 Chapter 3 Chemistry of Curbocufions

3.2.3 Experimental Examples of Formation of a Carbenium Ion

by Abstraction of a Hydride Ion H- from an Alkane
by a Brsnsted Superacid, with Formation of Hydrogen

The following overall hydride abstraction reaction:

+ H'S-
CnH2n+2 + (CnHZn+,)+S-+ H,
where S- represents the conjugate base anion of the superacid, was demonstrated for the first
time in 1963 by Oelderik [89], who revealed the formation of the ter-butyl carbocation by
reaction between isobutane and the superacid HF-SbF,. Shortly afterwards Hogeveen et al.
[88] and Olah et al. [43, 901 confirmed the possibility of obtaining carbocations directly
from alkanes in superacid medium. We have seen that some of these acid media, e.g. HF-
SbF, and HFS0,-SbF,, are tens of millions of times stronger than concentrated sulphuric
acid (H,, = -12). With this type of medium, the proton can associate with a oC-H bond and
destabilise this bond by attraction and transfer of the electron pair.
With isobutane, the reaction occurs in two steps, firstly protonation of the alkane into a
short-lived carbonium ion, then split of this ion into a carbenium ion and hydrogen [63]. This
protolysis reaction is outlined in figure 3.6.
In this type of reaction, which consists of extracting a hydride ion H- from the paraffin,
the oC-H bond belongs to a tertiary carbon and the reaction can take place at very low tem-
perature (40OC). Olah also describes the possibility of activating a C-H bond on a primary
carbon by carrying out the reaction at a higher temperature (SOOC), as with methane which
is converted into ter-butyl cation by a series of attacks of the C-H bonds of an initial mole-
cule of methane by methyl (the methyl carbocation is highly unstable by nature, therefore
very acidic), then alkyl carbocations, with elimination of hydrogen (fig. 3.7).
The formation of the persistent ter-butyl ion in superacid protic medium was observed
for the first time by Olah in the early sixties [3a, 3b] and widely confirmed later [46, 88,91,
921. Results obtained at the IFP in the seventies, when studying conversions of alkanes (iso-
merisation and cracking) in the presence of Brensted superacids [91, 921, confirm that the
ter-butyl tertiary carbocation is a persistent species in this type of medium, that it is found
in high concentrations, that these carbocations can be titrated and that their concentrations
are governed by equilibria which depend on the operating conditions.
In this study, the superacid medium used is the liquid mixture HF-SbF, obtained by
introducing SbF, in anhydrous hydrofluoric acid, mixture in which alkanes are not very sol-
uble. The two liquid phases (acid and hydrocarbon) are stirred with a turbine. The experi-
ments are carried out between -15 and 40°C, in closed reactor, monitoring firstly the
changes in the organic phase and the organic species dissolved in the acid phase, by chro-
matographic analysis and secondly the increase in pressure of the reactor due to release of
hydrogen.
To determine the type and quantity of the hydrocarbons and carbocations present in
superacid solution, we start by drawing off the hydrocarbon phase with a diving tube. The
acid phase is then washed with a fairly unreactive hydrocarbon (n-butane or propane). To
obtain the type and quantity of the carbocations, excess methylcyclopentane is added to the
 Chapter 3 Chemistry of Carbocations 141

acid phase to convert the carbocations by hydride exchange into the corresponding alkanes
(fig. 3.8). These alkanes are extracted from the acid phase by the excess methylcyclopentane
and can be analysed by chromatography.

Fig. 3.6 [43,88-901

Abstraction of a hydride ion H- from an alkane by the Brsnsted superacids HF-
SbF, [88,89] or HSO,F-SbF, [43,90] with production of hydrogen.

Fig. 3.7
Formation of the ter-butyl cation by reaction of methane in the superacid
HF-SbF, at 80°C.

+ R+ SbF; + RH + flcH3SbF;

Fig. 3.0
Hydride exchange between methylcyclopentane and a carbenium ion R+

When the alkane studied is isobutane (LC,H,,,), the ter-butyl cation (t-C,H; or t-Cqf) is
produced by the equilibrium reaction of figure 3.6 with simultaneous release of hydrogen.
Figure 3.9 shows that the ter-butyl cation and the hydrogen are formed in stoichiometric
quantities.
142 Chapter 3 Chemistry of Carbocations

[SbF,]: 1.12-4.7 moVl

T : 5-40°C

r-----------

I I !
L
2 4 8
Number of f-Cd or t-C; ions formed (x 10-2 mol)

Fig. 3.9 [92]

~~

Linear relation obtained between the quantity of hydrogen released and the
quantity of ter-butyl ions (t-Ci = t-C4Hi) or t-Cl formed.

The influence of various operating conditions (SbF, concentration, hydrogen temperature

and pressure) is as follows:
SbF, concentration.The ter-butyl cation concentration increases with the SbF, concentration
to reach significant values, in the region of 2 moVl or approximately 10% by weight (fig. 3.10).
Temperature. The tev-butyl cation concentration increases with temperature, indicating
that the reaction is endothermic (fig. 3.1 1).
Hydrogen pressure. The results show that by increasing the hydrogen pressure, the car-
bocation concentration decreases (fig. 3.12). This confirms that the reaction shown above is
well balanced and that, in addition, the carbocations are sufficiently active at 5°C to react
with hydrogen according to the equilibrium reaction:
t-C4H,f + H, @ i-C4H,, + Hi
This equilibrium is governed by a constant K:

K = [I'-C4H 10 "
+ 1
[t-Cil. PH2
 LIVE GRAPH
Click here to view

Chapter 3 Chemistry of Carbocations 143

Feedstock: iC4Hj0, P,. = 0.85 MPa

2.0 -+- tC4 for T = 5°C

L
h

-2
v

0
+ tCf for T = 30°C
+ iC4H10 dissolved
2
Y
1.5

-2
Q
+P

y
Y
1.0
U
-
2
H 0.5

a 1 2 3 4 5
[SbF,] (molil)

rig. J.IU IYLI

Influence of the SbF, concentration on the concentration in ter-butyl ion
(t-Cd = t-C4Hi) formed and in isobutane (i-C4Hl0)dissolved.

LIVE GRAPH
Feedstock: i-C,Hio Click here to view

-0- t-Cf for [SbF,] = 3.9 molil

+ f-Ci for [SbF,] = 1.2 molA
-+- iC4H,o dissolved
PH,= 0.96 MPa

0
-1 5 0 15 30 40
Temperature (“C)

Fig. 3.11 [92]

Influence of the temperature on the concentration in ter-butyl ion (t-Cd
= t-C4H;) formed and in isobutane (CC4H,,) dissolved.
144 Chapter 3 Chemistry of Carbocations

LIVE GRAPH
Click here to view
hence:

Figure 3.12 shows that this last relation is well satisfied.

0.8

-
5?
4
$ 0.4
.-K
E
.-c
c
E
50 0.2
0
E

0 0
0 0.5 1 .o 1.5 2.0
Hydrogen pressure (MPa)

RH = kC4H10, [SbF,] = 2.5 moVl 0 t-C;from rrC,Hl,

T = 5°C 0 t-C;from kC,Hl,

Fig. 3.12 [92]

Influenceof hydrogen pressure on the quantity of ter-butyl ions (i-Cd = t-C4H;)
formed from CC4Hlo(or t-Cf = t-C,H:, formed from n-C,H,, or i-C5H,J.

3.3 STABILITY, STABlLlSATlON AND REACTIVITY OF CARBOCATIONS

3.3.1 Stability of Carbocations

The stability of hydrocarbon-containing ions depends on factors which are both internal
(size, configuration, electron structure of the ion) and external (immediate environment of
the ion). These factors act favourably when they offer better charge delocalisation either on
the whole of the ion itself for the first, or to external partner entities (counter-ion, solvent
molecules) for the second. The internal factors include:
 Chapter 3 Chemistry of Carbocations 145

- the resonance effects: the presence of unsaturation near the charge may, by delocalis-
ing it, have a strong stabilising effect on the carbocation (with for example allyl, ben-
zylic and tropylium carbenium ions, etc.);
- the inductive effects due to the presence in the molecule of electroattractive groups
*
(CI > Br, 0, S > I N, C, H). The polarisation by inductive effect of a bond decreases
rapidly with distance (it generally becomes negligible from the third carbon atom).
The main external factors are:
- The presence of a counter-ion which neutralises more or less the charge of the carbo-

cation. For example, in the superacid HF-SbF,, the ter-butyl carbocation is stabilised
by the proximity of the slightly basic counter-anion Sb&. In the pores of a zeolite, we
might expect that the carbocations are more or less stabilised depending on their
degree of interaction with the negatively charged framework.
- The solvent effect. In liquid medium, the molecules of a polar solvent surround the ion
and stabilise it. The zeolites with highly charged framework (aluminium-rich
aluminosilicates) develop electrostatic fields in their pores which may favour the for-
mation of carbocations (the zeolites have been compared to solid solvents).
The carbocation can be considered as an unstable short-lived species (apart from some
carbenium ions in the presence of strong acids or, generally, superacids), which prefers to
minimise its energy by combination with a counter-ion to form a partially covalent bond. We
will first examine this point before discussing the relative stability of some of the most well-
known carbenium ions and that of the carbonium ions.

3.3.1.I Carbenium Ion is a Generally Unstable Reaction Intermediate

Direct experimental observation of carbenium ions is difficult. Although it is possible with
some persistent ions in superacid medium, it is very difficult with the acid solid catalysts:
the octenium secondary ion formed at 20°C on H-ZSM-5 from octene has not been detected
by NMR of 13C[93],but the diphenylethenium tertiary ion has been observed on zeolite Ca-
Y at ambient temperature by UV-visible spectroscopy [94].
Theoretical calculations [95-991 and various experimental characterisations [ 1001 indi-
cate that, at the surface of an acid oxide (silica-alumina, zeolite, etc.), the carbenium ions
are not free but are more or less strongly adsorbed, and therefore stabilised as alkoxides or
species linked to the oxide by a hydrogen bond. As shown on figure 3.13, these two forms
would be in equilibrium, the alkoxide form being favoured at low temperature [66, 1021. The
alkoxide, considered as being the stabilised form of the carbenium ion [66,95,96, 101, 103-
1121, is characterised by a more or less pronounced degree of covalence of the C-O bond,
depending on the case [lo], 1041. The same applies with non-superacid liquid acids:
butenes, for example, react with concentrated sulphuric acid at room temperature to form
butyl esters, the butyl carbocation only being short-lived.According to Kazanski [ 104, 1051,
the intermediate active species present on the various acid solids are significantly different
from the protonated ionic states formed in aqueous solution, being more like the complexes
formed by acid and base interaction in non-polar solvents. The heterolytic dissociation state
is only observed persistently in liquid medium with polar solvents, due to the stabilisation
of ionic species by solvation [1Q8]. Carbenium ion only seems to exist as an unstable, more
or less fugitive form on the surface of acid solids [104, 105, 1081. There are several possi-
146 Chapter 3 Chemistry of Carbocations

ti
\ CH3
/‘C% /H I
I
H’ c\H
I
0 0
/ \
\o/ \o/
rr complex (r complex

Fig. 3.13 [ 1011

Alkoxides forms of the ethyl carbenium ion: from the A complex to the o com-
plex via an intermediate form.

ble reasons for heterolytic rupture of the C-0 bond (where 0 is an oxygen of an acid solid
oxide) which produces the unstable “negative surface-carbocation” ion pair [ 1051:
- the pronounced tendency of the product of the acid-base reaction to form electrostatic

bonds;
- temperature, temperature rise weakening the C-0 bond;

- stabilisation of the cation near the solid anion [ 1031.

Only the most naturally stable carbocations (e.g. triphenylcarbenium ion) or those sta-
bilised in superacid media (some tertiary carbenium ions) can be observed (using NMR, for
example) at ambient, or even lower, temperatures. Less stable carbocations or those less sta-
bilised by their counter-ion (anion from the acid partner) can only be observed at higher tem-
peratures. Consequently, in heterogeneous acid catalysis, the free carbenium ion is generally
difficult to observe and must be considered as a reaction intermediate (corresponding to a
high-energy potential well), more or less short-lived [ l , 103, 104, 1081 depending on its
structure, its reactivity, the type of the neighbouring site (especially the strength of the site)
and the conditions of the medium (especially the temperature).
The conversion of one hydrocarbon into another hydrocarbon by acid catalysis involves
several carbocationic reaction intermediates. Strictly, the true activated complex correspon-
ding to the most unstable state reached during the reaction is not the carbocation itself but
an activated state of the carbocation (possibly located in a potential well), which is an unsta-
ble transition state, intermediary between the reactant carbocation and the product carboca-
tion. This is illustrated on figure 3.14 which positions schematically in an energy diagram
the normal and isomerised carbenium ions and the corresponding activated states which are
the most unstable with respect to the non-ionic species physically or chemically adsorbed on
a site, using gaseous reactants [ 101, 109, 112, 1131.
This description is still probably a simplified vision of the true situation. Kazanski [ 1081
in fact considers that the acido-basic reactions do not necessarily involve ionic transition
states but instead take side-tracks involving concerted mechanisms to avoid the need for an
unstable intermediate carbocation. Consequently, without fidly rejecting the formation of
 Chapter 3 Chemistty of Carbocations 147

alkylcarbonium ions (non-classical carbocations) in liquid superacid medium, Kazanski

[ 1081 is sceptical regarding the possibility of forming such an ion with an acid solid, it being
particularly unstable due to the low protonic affinity of paraffins; he proposes, for example,
a concerted mechanism for the protolysis reaction of propane on an acid zeolite (fig. 3.15).
This type of synchronised mechanism could also explain the H-D exchange, which is
easy between acid solids and alkanes (fig. 3.16).

n-C; gas

I, R-CL physically
adsorbed

x complex
CC; physically
adsorbed
i-CL gas

x complex
R-alkoxy species

R-6complex
i-ocomplex
Fig. 3.14
Simplified representation in an energy diagram of the main intermediate tran-
sition states in the isomerisation of a linear olefin n - C i (n-C,H2,).

Possible concerted mechanism for protolysis of propane on zeolite.

Possible concerted mechanism for H-D exchange on a zeolite (R: hydrogen or

alkyl group, 0: oxygen on the surface of the solid).
148 Chapter 3 Chemistry o/Curbocutions

However, various experimental arguments, published many years ago with the liquid
superacids [ 1 14, 1161 and more recently with the acid solids [ 1 171, describe this exchange
as involving a carbonium ion intermediate:
OD + CR,H + 0-(CR,HD)' + OH + CR,D
Without underestimating the existence of these concerted mechanisms, in the remainder
of this book we will focus on the notions of carbenium and carbonium ions, as well as their
corresponding formalism, to describe the numerous conversions possible with hydrocarbon-
containing molecules in petrochemistry and refining. Although somewhat simplified, the
advantage of this description is that it provides a coherent and rational presentation of the
large and complex category of these conversions.

3.3.1.2 Relative Stability of Carbenium Ions [118-1241

The stability of the carbenium ion R+ can be expressed either in a unique stability scale or
with respect to the hydrocarbon-containingmolecules it came from ("parent molecules").
The unique scale can be drawn up from the standard heat of formation of the ions. It cor-
responds to the heat of reaction (under standard conditions: 25"C, atmospheric pressure)
leading to the formation of the ion considered from pure elements, taken in their standard
state (the standard heat of formation of these elements is, by definition, equal to 0).
Knowing the standard heats of formation APf(R+) of the ions, we can compare the stabili-
ties of a wide range of cations in a unique scale, but the carbocation stability values found
in scientific literature are rarely expressed in this way.
Since carbocation stability values are generally expressed as relative to those of the par-
ent hydrocarbons, they cannot be compared together directly. Their values correspond to the
free enthalpy variation of the reaction producing them in gaseous phase (the immediate envi-
ronment of the ion can then be neglected) from a parent molecule. The reaction used may
be, for example, protonation of an unsaturated hydrocarbon or heterolytic dissociation of a
saturated hydrocarbon-containing compound. In view of the low entropy variation
(T. AS = 3 kcal/mol to 7 kcal/mol), we consider that the formation enthalpy AHf, between
160 kcal/mol and 270 kcal/mol, is a fairly good representation of the stability of a carbe-
nium ion with respect to the initial hydrocarbon.
In the first case (protonation), we measure the protonic affinities of alkenes and benzene
derivatives, for example. This method was used in particular to collate a large number of val-
ues of the relative heat of formation of carbenium ions [ 1241.
In the second case (heterolytic dissociation), experimental determination of the ion sta-
bility uses the following general reaction, combining an ionisation reaction and a dissocia-
tion reaction:
AB + AB' + A+ + B
The heat of formation of the ion A+ is expressed from the relation:
AHXAB) = AHXA') + AHXB) - AHR
where AHR may be taken, to a first approximation, to be the minimum energy required to
ionise AB, known as appearance potential.
 Chapter 3 Chemistry of Carbocations 149

Hence the heat of formation of the ion A':

AHAA') = AHAAB) - AHXB) + AHR

If, for example, AB is a saturated hydrocarbon RH, the ion Rf will be formed, according
to this sequence, firstly by losing an electron, then by homolytic scission of the R-H bond:
RH -+ RH' + R+ + H'
AHXR') = AHXRH) - AHAH') +AHR
where: AHXH') = 0 by definition
However, the stability of a carbenium ion R' is also frequently expressed by considering
the neutralisation reaction of the ion which forms RH by capture of a hydride ion. The oppo-
site reaction, i.e. heterolytic dissociation of RH, is obviously different from heterolytic
dissociation with prior ionisation, discussed above. The R+ neutralisation reaction is written:
R' + H- & RH
and the stability of the corresponding ion R' is expressed by the affinityA$ of the ion R'
for the hydride ion H-:
A; = AHXRH)- AHXR') - AHAH-)
The affinity of carbenium ions for the hydride ion H- measures their tendency to desorb
as alkanes and therefore expresses their relative stability with respect with the corresponding
paraffin.
The values of AHAR') and A :: given in table 3.1 can be used to compare the stabilities
of various carbenium ions with respect to the parent hydrocarbon. Since the reference is dif-
ferent in most cases, these values cannot be used to compare the ion stabilities directly.

A. Saturated Carbenium Ions (Existence of CT Bonds Only)

(tables 3.1 and 3.2) [3, 118-122, 124-1281
a. Acyclic Ions
We have known for some considerable time that tertiary carbenium ions are more stable than
secondary carbenium ions, which are in turn more stable than primary carbenium ions. The
least stable carbenium ion is the methyl ion CH;. Table 3.2 shows the energy differences
between the methyl and ethyl primary ions, the sec-propyl secondary ion s-C3H;f and the ter-
tiobutyl tertiary ion t-C,H;, in gaseous phase or solvated, estimated by various authors.
In spite of the dispersion of values obtained according to the authors, the increasing order
of stabilities can be written unambiguously:
tertiary > secondary >> primary >>> methyl
CRf CR,H' CRH; CH$
The improved stability resulting from an increase in the degree of substitution of the car-
bon carrying the charge is due to greater charge delocalisation over the whole ion. With
hydrocarbon ions, this delocalisation is favoured by the presence of CT bond electron donor
(weakly) groups. In particular, a methyl group is a stronger electron donor than the hydro-
150 Chapter 3 Chenristry ofcurboculions

gen atom H' and its presence near the carbon carrying the positive charge of the ion
increases the stability of the ion. This stabilisation mode, which results from the interaction
between the vacant p orbital of the charged carbon and the CJ bond(s) located in CJ position
from this carbon, is called 0 stabilisation or hyperconjuguation.
For carbenium ions with the same hydrocarbon-containing skeleton, the stability differ-
ence would be 54 kJ/mol between tertiary and secondary and about 71 kJ/mol between sec-
ondary and primary [ 1211. Amongst the alkylcarbeniums C4H&the ter-butyl tertiary cation
is 67 kJ/mol more stable than the see-butyl secondary cation and 130 and 138 kJ/mol more
stable than the isobutyl and n-butyl primary cations respectively [ 1221.
The stability of a carbenium ion depends on several factors:
- the degree of substitution of the carbon carrying the charge, as described above;
- the number of carbons in the ion (tables 3.1 and 3.2): at 298 K, the stability of an ion
increases with its number of carbons [118, 122, 1231. This stability classification
depends on the temperature, however. At a higher temperature, the ter-butyl ion
appears to be the most stable alkylcarbenium [43]: in the superacids, for example,
some heavy tertiary carbocdtions with at least 6 carbons decompose above 353 K
(SOOC), producing the ter-butyl cation [90] ;
- the type of alkyl substituents and especially the number of C-C bonds that a sub-

stituent places in p position with respect to the positively charged carbon: an ethyl
substituent fixed to the positive carbon is more stabilising than a methyl group.
The classification of intrinsic reactivities of carbenium ions is obviously the opposite of that
of their stabilities: the reactivity of primary ions with respect to a hydride is much greater than
that of the secondary ions, in turn greater than that of the tertiary ions. By analogy with the
lability and reactivity of the proton of a Brransted acid site, the ease of desorption of these ions
as paraffins (by hydride transfer) and their reactivity therefore decrease in the following order:
primary ions secondary ions > tertiary ions

b. Cychc lons [3, 119, 1201

Numerous structures of cyclic carbenium ions are described and discussed in the books writ-
ten by G.K. Surya Prakash and P.v.R. Schleyer [3b], by X. Creary [ 1191 and J.M. Coxon
[ 1201. We will take a brief look at some of the most well-known of them.
Whilst the stability rules of saturated cyclic carbenium ions are similar to those of alkyl-
carbenium ions, they are affected by the steric constraints (bond angles, difficulty of meet-
ing the flatness requirement of carbenium ions) present especially in small rings (15 carbon
atoms) or some multicyclic structures. These steric constraints affect not only the stability
but also the structures of the cyclic carbenium ions: some may oscillate between several
shapes of similar energy but belonging to different categories of ions: classical (carbenium
ions) or non-classical (carbonium ions). Consequently some of these structures remained
uncertain for a considerable time, others are still imprecise even now.
For example, the structure of the cyclobutyl cation C,Hf was only determined during the
1980's. The best representation of this structure is that of an equilibrium by rapid inter-
conversion between the following two C4Hf ions (fig. 3.17), which have very similar ener-
gies: the cyclopropylcarbinylcarbenium ion (CyC3CH;), whose charge is not carried by the
 Chapter 3 Chemistry of Carbocations 151

ring, and the bicyclobutonium ion CyC4H; which, strictly speaking, is a carbonium ion [3b,
3d]. The latter ion may also be represented as two cyclopropane type rings, joined along one
edge, and on which a proton is delocalised.

Table 3.1 Heats of formation AHXR') and affinity A: values for the hydride ion, a few ions
corresponding to paraffins, naphthenes and various unsaturated hydrocarbons [ 1 18a, 1241.

Heats of formation Affinity' for the hydride ion

Carbenium ion AHF(R+) Ag
(kcal/mol) (kcal/mol)
References
CH3+ 258 26 1 313
C2H5+ 225 216 270
A+
*
218 207 267
194 192 25 1
200 200 265
190 I83 246-248

A 1 74 167 233

M 181 173 247

162 - 23 1

Cyclobutyl ion 213 - -

Cyclopentyl ion
O+ 195 - 250

Cyclohexyl ion
0. 187

235
-

-
-

229 -

203 -

205 -

235 - 244

1. In gaseous phase in standard conditions.

152 Chapter 3 Chemistry of Carbocarions

Tableau 3.1 (continued).

257

192

Table 3.2 Stability differences between primary, secondary and tertiary carbenium ions in kcal/mol
[125].

Franklin Franklin- Oosterhoff Franklin

Energy Lumpkin
difference [ 1261 11281 [I 18a]
(kcaUmol) ~ 7 1
between
Gas Solv. Gas Gas Soh. Gas
C,H;/CH; 38 31 36 34 30 33
s-C3H;/C,H; 36 28 30 32 28 31
t-C,H~/s-C,H~ 22 16 18 13 8 20

Fig. 3.17
The cyclobutyl ion represented as an equilibrium between the structures of
cyclopropylcarbinyl and bicyclobutonium ions.

The case of the cyclopentyl and cyclohexyl carbenium ions, which are important for their
role in refining and petrochemistry, is simpler. Amongst the various possible structures of
the cyclopentyl ion, the most stable is that where a C-H bond of each carbon next to the pos-
itive carbon is nearly parallel to the vacant p orbital of this carbon (fig. 3.18). In this posi-
tion a hydride can move easily from one carbon to the next, with simultaneous shift of the
positive charge, resulting in dynamic equilibrium between five mesomer forms of the ion.
The structure of the cyclohexyl ion can be represented as an equilibrium between two ionic
forms, either both chair type or one chair, the other boat [3e].
 Chapter 3 Chemistty of Carbocations 153

Fin. 3.18
Most stable form of the possible structures of the cyclopentyl ion (two C-H
bonds are almost parallel to the vacant p orbital of the unsaturated carbon).

Table 3.1 shows that these two secondary cyclic ions have quite low stabilities, similar to
those of the secondary alkylcarbenium ions. The secondary cyclohexyl ion can quickly
rearrange itself into the much more stable tertiary methylcyclopentyl ion.
The case of ions with several rings, especially the 2-norbornyl and adamantyl carboca-
tions, is more complex.
The structure of the 2-norbornyl carbocation C,Hfl has been a centre of controversy since
the middle of the 20th century [3b, 3 4 1191. The most recent data point to a non-classical
bridged structure of carbonium ion type, represented on figure 3.19a. In this structure,
which is different from that of the classical carbenium ion (fig. 3.19b), and also more sta-
ble, the cation adopts a more spherical symmetry, the charge being delocalised on 3 bonded
carbons which form a protonated cyclopropane type ring.

a. b.

7
7

Fig. 3.19
5 p’i
6
I’ + ‘\

Non-classical (a) and classical (b) structures of the 2-norbornyl carbocation C,H: I .

The adamantyl carbocation CloHt5,prepared for the first time by Olah and Schleyer, is
stable in superacid medium [3b, 1191. It consists of polycyclic carbocation with 4 hexago-
154 Chapter 3 Chemistry of Carbocations

nal gauche sides joined such that each one shares 3 carbon atoms with each of its 3 neigh-
bours (fig. 3.20). Although it is not planar, this ion is stable since the 3 C-C bonds located
in p position are parallel with respect to the vacant p orbital of the positive carbon atom,
which favours stabilisation by hyperconjugation.

6 4

Fig. 3.20
Structure of the adamantyl carbocation C,oH:5.

B. Unsaturated Carbenium Ions (Presence of 71 Bonds)

a. Acyclic Ions
The values representing the stabilities of these ions, given in table 3.1, are difficult to com-
pare together and with those relating to saturated carbenium ions, since they depend to a
large extent on the heats of formation of the parent hydrocarbons which vary significantly
with the structure and whether or not there is resonance energy. In spite of the deceptive
values in this table, we know that the primary allyl carbenium ions are much more stable
than their saturated counterparts, since the presence of a double bond in p position with
respect to the positively charged carbon allows, by resonance, charge delocalisation which
improves the stability of the cation. The stability is obviously increased by the presence of
a substituent alkyl group on the positively charged carbon, since the carbocation is then
secondary.
The stability of vinyl ions also depends on the number of substituents on the positively
charged carbon. The primary vinyl ion resulting from the protonation of acetylene is there-
fore highly unstable at ambient temperature, more unstable in particular than the ethyl car-
benium ion [ 1221 and much more unstable than the allyl primary cation. The secondary vinyl
ion, however, formed from propyne, has a calculated stability similar to that of its isomer,
the corresponding primary allyl ion [ 1 18al. The stabilisation of the vinyl carbocation
CHR=C+-R also depends on the types of substituent present on the carbons of the double
bond. It is greater if the R groups are aryls (n: type stabilisation), as with the phenyl-I-vinyl
cation (CHR=C'-Ar), than if they are alkyl type (0 type stabilisation).

b. Cyclic Ions
For the unsaturated rings, the stability of the carbenium ion is closely related to the value of
the resonance energy introduced by the double bond(s) present.
 Chapter 3 Chemistty of Carbocations 155

With monocyclic structures, this resonance energy, or degree of aromaticity, is the key
parameter [I]: Huckel’s semi-empirical rule [ 1291, proposed in 1931, states that the aromatic
structures (ionic or neutral) necessarily contain 4n+2 x-electrons (when n = 0, 1, 2, 3, 4...
there are 2, 6, 10, 14, 18... x electrons respectively).
This rule can be used to predict (verified by theoretical calculations) that the following
ionic structures are stable [I]:
- the cyclopropenyl (2 It-electrons in the 3-carbon ring) and triphenylcyclopropenyl
cations, and especially the tripropylcyclopropenyl carbocation, which would appear to
be one of the most stable known carbenium ions, possibly even the most stable
(fig. 3.21a and b);
- the tropylium cation or cycloheptatrienyl cation (fig. 3.21c), a cation with 6 x-elec-
trons, but with a 7-carbon ring, would have the most stable configuration just after that
of the tripropylcyclopropenyl ion; in particular, it would be slightly more stable than
the primary benzyl carbocation isomer [ 1301. In liquid phase, its formation is easy and
has been known for many years. In gaseous phase, its formation has been deduced
from results obtained with various alkylaromatics such as toluene, xylenes, ethylben-
zene and alkylaromatics substituted by chlorine [ 113, 1 18a, 118b, 130-1371.
Huckel’s rule can also be used to predict that cyclopentadienyl carbenium ions and sub-
stituted ions, such as the pentaphenylcyclopentadienyl ion, are not very stable since not aro-
matic (4 It-electrons in the 5-carbon ring).

a.

b.
C6H5 C
, 6H5 CH3CH2CH2
\ \ /CH2CH2CH3
c=c c=c
\ I
C+
I
- etc.
\ I
C+
I
- etc.

C6H5 CH2CH2CH3

Fig. 3.21
Aromatic cyclic ions: cyclopropenyl cations (a), triphenylcyclopropenyl and
tripropylcyclopropenyl cations (b), two C,H; ions: benzyl and tropylium (c).
156 Chapter 3 Chemistry of Carbocations

Although it is not strictly speaking a cyclic ion, the benzyl primary carbocation
C6H,-CHi is worth mentioning briefly here due to its relation with the tropylium ion
(fig. 3.21~).Due to the proximity of the 6-carbon aromatic ring, the stability of this ion is at
least equivalent to that of the ally1 carbocations. Calculation shows that its formation energy
is close to that of the tropylium ion, whose high (relative) stability had been predicted by
Huckel [129]. Strangely enough, attempts to identify the benzyl carbocation using isotope
marking led to the conclusion that the 7 carbons of this cation have the same behaviour
[ 1301. Meyerson et al. [ 1301 appear to have been the first to propose that the true structure
of the benzyl ion is rather that of the tropylium ion, where the 7 carbons are included in the
ring and become equivalent [ 1 13, 118a, 1 18b, 130-1341. Siege1 [ 1321 reaches similar con-
clusions without dismissing, however, the possibility that the two isomer structures
(table 3.1) exist and can switch very rapidly from one to the other (fig. 3.21~).Identification
of the benzyl cation using the tropylium ion could explain why the phenyl ion C6Hf is
strongly stabilised by the presence of a methyl substituent on the aromatic ring (benzyl or
tropylium ion), whilst a second methyl substituent produces virtually no further stabilisation
[ 1301. Note that the rearrangement of the benzyl ion into the tropylium ion would only have
been observed in gaseous phase, not in solution [ 1381.
Concerning the benzyl carbocations, their stability in liquid phase increases with the
number of aryl groups attached to the cationic centre [120a], i.e. in the following order:

triphenylmethyl cation > diphenylmethyl cation > primary benzyl cation Ph-CH,f
The benzyl cations are generally more stable than the tertiary carbenium ions [ 120al. The
triphenylmethyl ion is known for its high stability (or persistence) in liquid medium. The pri-
mary benzyl carbocation has only been identified by NMR in superacid medium [ 1201.

C. Dications
The carbenium dications only appear to have been observed in a limited number of cases.
Figure 3.22 [ 1241 shows the structure of some simple persistent dications, identified in solu-
tion. Other dications of more complex structure have recently been described in the litera-
ture, e.g. the tetraphenyl-p-xylyl or tetraphenyl-m-xylyl dications which have the same
overall formula Ph2-C+-Ph<fPh2 [3gJ, and the pagodyl dication formed by oxidation of
pagodane in superacid medium [3g].

Fig. 3.22 [ 1241

Structure of some dications.

None of the conversions examined below involves dications.

 Chapter 3 Chemistry of Carbocations 157

D. Stability Classification of Carbenium Ions

In liquid phase, the carbenium ions are classified in the order shown on figure 3.23: the
tripropylcyclopropenylcation is the most stable, followed by the tropylium, tnphenylcarbe-
nium, benzyl, ally1 and tertiary alkylcarbenium, secondary, primary alkylcarbenium and
methyl ions. Note that, at low temperature, the vinyl ion and the phenyl ion (which is
obtained by abstraction of a hydride from benzene) are very unstable and comparable with
the methyl ion. This classification is not necessarily the same at the frequently high temper-
atures (300 to 550°C) used in heterogeneous acid catalysis. For example, in view of what we
have seen in the previous paragraph (3.3.1.2.B.b), the stabilities of the tropylium and benzyl
ions are quite close in gaseous phase.

Tripropylcyclopropenyl Cycloheptatrienyl Triphenylcarbenium Benzyl

cation cation ion cation
(tropylium) (trityl)

CH3 H
I I
CH,=CHCH; , CH3-7' > CH3-C+ > CH,-CH;
I
CH3 CH3
Ally1 f-butyl lsopropyl Ethyl
cation cation cation cation

H H
Methyl Vinyl Phenyl
cation cation cation

Fig. 3.23
Classification by order of stability in liquid phase of various carbenium ions.

3.3.1.3 Stability of Carbonium Ions

Carbonium ions are by nature unstable. Kazansky [ 104, 1051 says that many of them are
highly excited complexes with very short lifetime. Apart from a few exceptions, it is diffi-
158 Chapter 3 Chemistry of Carbocations

cult to compare their stabilities with those of carbenium ions, due to insufficient data.
Figure 3.24 [ 1221 ranks by relative stability various alkylcarbenium ions and some alicyclic
carbonium ions derived from the protonated cyclopropane ion. According to this figure, pro-
tonated cyclopropane ions with few substituents (one or two) would have, for an equivalent
number of carbons, stabilities in between those of the secondary and primary alkylcarbe-
nium ions. Those with a greater number of substituents are more stable than the secondary
alkylcarbenium ions.
Overall, the stability rules are similar to those of the corresponding carbenium ions. For
example, the stability of the alkylcarbonium ion increases with its number of carbons and
the degree of substitution of the carbon carrying the charge. For instance, the protonic affini-
ties in gaseous phase of methane, ethane, propane and butane are respectively 532,552-588,
6 19-640 and 687-698 kJ/mol [66]. Concerning the protonated cyclopropane and cyclobu-
tane ions, Condon [ 1391 considers that the factors involved in their stability are the same as
those involved in the stability of the cyclopropane and cyclobutane hydrocarbons; the num-
ber of alkyl groups carried by these rings, i.e. the number of tertiary carbons on the ring, is
one of these factors.

"I 0
kJ/mol

I I I b
3 4 5 6 7
Number of carbons

Fig. 3.24 [ 1221

Relative stabilities of various alkylcarbenium and alicyclic carbonium ions in
gaseous phase (C, and C,) and in liquid superacids (C, to C7). H: relative
enthalpies.
 Chapter 3 Chemistry of Carbocations 159

The increase in stability provided by any further substituent on the charged carbon is,
however, less than that observed with carbenium ions, since the charged carbon of the car-
bonium ion is already more substituted initially than the carbenium ion [ 1221.
Authors are not unanimous regarding the relative stabilities of the various isomer carbo-
nium ions which may form by protonation of an alkane. Some [ 1401 propose, on the basis
of results obtained by chlorination of a linear alkane, that protonation occurs preferentially
on the penultimate (last but one) secondary C-H bond and very rarely on the primary C-H
bonds and the interior and terminal C-C bonds. The theoretical calculations by other
authors show that the 2C 1H bonds (fixation of a proton on a C-C bond) are more stable
than the 1C2H bonds (fixation of a proton on a C-H bond) [66]. The energy differences
between these two bonds would increase as the size of the cation decreases: 11,21-38 and
3 1-50 kJ/mol for n-butane, propane and ethane respectively [66]. The ethonium carbonium
ion exists in the two isomer forms of figure 3.25, calculations showing that the first is more
stable [ 1041.

,'H' *
,? .
I
,
+.
%

CH3---- CH3 or CH3-CH2 --+--'H

Fig. 3.25
Isomer forms of the ethonium carbonium ion.

3.3.2 Stabilisation and Reactivity of Carbocations

3.3.2.1 Stabilisation of Carbenium Ions by Interaction with their Environment

The stability of a carbenium ion not only depends on the previous internal factors, but also
on external factors. Its stability in the acid medium which produced it depends in fact on the
more or less stabilising environment it finds there. This environment may differ widely from
one acid medium to another, for example when changing from a gaseous medium to a liq-
uid medium. Generally, the stability of the carbenium ion depends on the nucleophilicity of
the medium in which it is present, i.e. the interactions of the charge with this medium: the
greater the possibility for the ion to delocalise this charge on other surrounding species, the
more stabilised it will be.
To reduce the effective charge of an ion by interaction with its surrounding molecules,
the most obvious method is the association of the carbenium ion with one or more ions of
opposite charge which reduce its effective electrostatic influence. This is the case with liq-
uid superacid media, where the carbenium ion is surrounded by counter-ions generated by
these acids. It is also the case with acid solids, especially zeolites, where the transition states
- the carbenium ions - are stabilised by the proximity of the oxygen atoms in the frame-
work [ 1031.
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160 Chapter 3 Chemistty of Carbocations

Another method is the interaction with a solvent, which is to a certain extent the case with
carbenium ions obtained in solution. The formation of an ion pair from a neutral compound
and the separation of these ions (dissociation) are in fact strongly favoured by polar solvents,
which cause charge separation due to their high dielectric constant and stabilise the small
ions by solvation [l]. The solvent effect of zeolites [103, 141-1451 (see paragraph 2.2.1.4.C)
is included in this category. The solvation forces often supply most of the energy required to
form the carbenium ions. The Born simple relation gives a first approximation of the free
energy variation resulting from the movement of an ion of radius r from one solvent (of
dielectric constant E,) into another (E~),and has been used to compare the solvating powers
of various solvents with respect to ions:

This relation shows that:

- the greater the dielectric constant E, the greater the ion solvation energy;
- ions of small radius are more highly stabilised by solvation. The solvation energies of
the methyl, ethyl, primary propyl, secondary propyl and ter-butyl aliphatic carbenium
ions vary according to a Franklin's estimation, from 61 kcal/mol to 41 kcal/mol for
very acid solutions.

3.3.2.2 Reactivity of Carbocations

The conversion of a carbenium ion is intramolecular or bimolecular. When it is intramolec-
ular, its rate can be expressed simply as follows:

V = k.[R+]
where k is the intrinsic rate constant of the conversion and [R'] the carbenium ion concen-
tration.
The ion concentration is directly related to its stability with respect to desorption as a
hydrocarbon: the lower the tendency of the ion to give up its positive charge to its counter-
ion to reform a hydrocarbon, the higher its concentration in the medium.
The bimolecular conversion of a carbenium ion by reaction with a given substrate S is ini-
tially governed by an acido-basic interaction between an electron-deficient species, in this
case the carbenium ion (considered as a Lewis acid), and an electron-donor species (a base).
This conversion is governed by a rate equation which depends on the previous factors and
on the substrate concentration:
v = k . [ R + ] [S]

The rate constant k is a function of the intrinsic activity of the carbenium ion and of the
acido-basic complexation stability with the electron-donor centre of the substrate (olefinic,
aromatic .rc bonds, oC-C or C-H bond). Obviously, k may take different values depending
on the type of S.