The Ethyl Cation

The ethyl cation is the prototype system for demonstrating the effect of hyperconjugation. Consider classical CH3CH2 as a combination of a methyl group and a -CH2 centre. The group orbitals of the methyl group (equivalent to the MOs of NH3) include the 7CcH3-orbital shown schemat- 

The correct nodal characteristics in this case means that both orbitals have a nodal plane containing the connecting bond and perpendicular to the page in Fig. 3.18. This means that they can overlap strongly with each other to give the interaction diagram shown in Fig. 3.19. 

One consequence of the hyperconjugative overlap shown above is that electron density is removed from the CH-bond of the methyl group (and 

Hyperconjugation is the reason that highly substituted cations such as %utyl are very stable. Note also that carbon-carbon bonds generally hyperconjugate better than carbon-hydrogen bonds. 

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When usiag HF TaF ia a flow system for alkylation of excess ethane with ethylene (ia a 9 1 molar ratio), only / -butane was obtained isobutane was not detectable even by gas chromatography (72). Only direct O -alkylation can account for these results. If the ethyl cation alkylated ethylene, the reaction would proceed through butyl cations, inevitably lea ding also to the formation of isobutane (through /-butyl cation). 

Table 1. Relative energies E (kJ mol 1) of the ethyl cation dependent on calculation method used (data from 43) if not otherwise indicated)...

The equilibrium between a and b in Eq. (2) depends on the energies of both the structures. In Table 1 the relative energies of the ethyl cation in the structures a and b, calculated with different methods, are shown. 

All alkyl ions tested demonstrate a comparable behaviour independent of the sign of their charges. The decrease of the reaction enthalpies AH (11) with the change from the methyl to the ethyl cation (AAH (ll) = 165 kJ mol-1) and from the ethyl to the but-2-enyl cation (AAH°(11) = 117 kJ mol-1) corresponds to the increase of stability of these carbenium ions, which are expressed by the difference of their heats of formation (AAH f = —118 and AAHj = —42 kJ mol-1 90)) and of their hydride ion affinity (AHIA = 176 and 126 kJ mol-1 91)), respectively. 

The calculation of an activation barrier for the reactions (21) and (22) must not necessarily be considered as an error of the method. For example, the MINDO/3 calculated activation barrier for the attack of a methyl radical on ethene 137-138) which is comparable to the former reactions was confirmed by experiments 139). In contrast to a free proton (Eq. (20)) the methyl radical as well as the ethyl cation possess steric space need. For this reason, the calculation of repulsive interactions which are able to overcome the attractive forces at certain distances cannot be seen without doubt as faulty. 

The simplest primary alkyl cations, CHJ and C2H, are formed from methane and ethane, respectively, by SbPs—PHSO3 (Olah and Schlosberg, 1968 Olah et al., 1969) and by SbPs (Lukas and Kramer, 1971). In these cases, intermolecular electrophilic substitution of these ions at the precursor alkanes leads to oligocondensation products, e.g. tertiary butyl and hexyl ions. In the presence of carbon monoxide it has been found possible to intercept the intermediate CHJ and C2H quantitatively as oxocarbonium ions (Hogeveen et al., 1969 Hogeveen and Roobeek, 1972). The competition between the reactions of the ethyl cation with ethane and carbon monoxide, respectively, is illustrated by the following equations ... 

Figure 2. Probability density plots of the ethyl cation product, (a) from the unlabeled reaction, (b) CH2CH3 from the labeled reaction, and (c) CD3CH2 from the labeled reaction. The backward scattered ethyl cation is more probable in (b), while the forward scattered ethyl cation is more probable in (c). Reprinted from [39] with permission from Elsevier.

Loss of MeCH the ethyl cation (376), leads to a marked decrease in +ve charge adjacent to the reaction centre (had it actually been from the reaction centre itself the +ve value of p would have been much larger) this carbocationic intermediate (37 b) will then react rapidly with any available water to yield ethanol. 

Assuming that the parent ethyl bromide sample was at a temperature of 298.15 K, we can apply equation 4.17 to evaluate the standard enthalpy of formation of the ethyl cation ... 

Pfeiffer and Jewett (1970), however, have made ab initio calculations on the ethyl cation and report the charge distributions in Figure 4b for the most stable ethyl ion. Their calculations agree with Hoffmann s in predicting that the classical ethyl structure is more stable than a bridged structure, but their calculated charge distribution is entirely different. 

Figure 4. Calculated charge densities in the ethyl cation, (a) Hoffmann, 1964 (b) Pfeiffer and Jewett, 1970 (c) Sustmann et ai., 1969.

Many mechanistic implications have been discussed, but we will concentrate here only on the most important structures in the context of dihydrogen-cation complexes. Deuterium-labeled methane and methyl cations were employed to examine the scrambling and dissociation mechanisms. The protonated ethane decomposition yields the ethyl cation and dihydrogen. Under the assumption that the extra proton is associated with one carbon only, a kinetic model was devised to explain the experimental findings, such as H/D scrambling. ... 

Finally, two studies have reported on the reactions of carbocations with Mg atoms using mass spectrometry The types of products formed depend on the nature of the carbocation. The labeled methanium ion, CH4D+, reacts via proton transfer (equation 11), deuteron transfer (equation 12) and charge transfer (equation 13). The ethyl cation reacts via charge transfer (equation 14) while the tert-butyl cation reacts via proton transfer (equation 15). In all cases there was no evidence for formation of an organomagnesium species. 

The C—H—C bond is not linear, the angle being about 170° according to high-level MO calculations. Several bridged cycloalkyl carbocations of the type 2 have been prepared [236]. Complexes between a number of alkyl cations and alkanes have been detected in mass spectrometric experiments [235]. The nonclassical structure of the ethyl cation, 3, may be cited as another example of hydride bridging (for a discussion, see ref. 55). 

Fig. 22. CCSD (tzp, spherical) optimized structures for the bridged and classical forms of the ethyl cation used in NMR calculations. (Reprinted with permission from Ajith Perera et a . (123). Copyright 1995 American Chemical Society.)...

In the ethane-ethylene reaction in a flow system with short contact time, exclusive formation of n-butane takes place (longer exposure to the acid could result in isomerization). This indicates that a mechanism involving a trivalent butyl cation depicted in Eqs. (5.1)—(5.5) for conventional acid-catalyzed alkylations cannot be operative here. If a trivalent butyl cation were involved, the product would have included, if not exclusively, isobutane, since the 1- and 2-butyl cations would preferentially isomerize to the rm-butyl cation and thus yield isobutane [Eq. (5.9)]. It also follows that the mechanism cannot involve addition of ethyl cation to ethylene. Ethylene gives the ethyl cation on protonation, but because it is depleted in the excess superacid, no excess ethylene is available and the ethyl cation will consequently attack ethane via a pentacoordinated (three-center, two-electron) carbocation [Eq. (5.10)] ... 

The superacid-catalyzed reaction is thus alkylation of the methane with the ethyl cation. 

A proton donor can be classified as an electrophile and a proton acceptor as a nucleophile. For example, hydrogen chloride can transfer a proton to ethene to form the ethyl cation. Therefore hydrogen chloride functions as the electrophile, or acid, and ethene functions as the nucleophile, or base ... 

Of these, the methonium cation, CHr> , is formed in largest amounts,8 the ethyl cation, C2H5 , is next, and there is a smaller amount of the C3HS cation (2-propenyl cation Section 8-7B). These ions then react with the substance... 

A variety of other methods have been used to measure the /3-silicon stabilization of car-bocations. From gas-phase studies, Hajdasz and Squires50 derived a value of 39 kcal mol-1 for the stabilization of the cation Me3SiCH2CH2+ relative to the ethyl cation. This is in agreement with calculations by Ibrahim and Jorgenson39. Siehl and Kaufmann51 have used carbon-13 NMR spectroscopic data to give an indication of the /1-silyl stabilizing effect in some aryl vinyl cations. 

The phenyl cation (134) firstpostulated by Waters335 is a highly reactive species oflow stability and plays a fundamental role in organic chemistry—for example, in the chemistry of diazonium ions. According to gas-phase studies and calculations, its stability is between that of the ethyl cation and the vinyl cation.336 Since it is an extremely electrophilic and short-lived species, it could not be isolated or observed directly in the condensed phase. For example, solvolytic and dediazoniation studies under superacidic conditions by Faali et al.337,338 failed to find evidence of the intermediacy of the phenyl cation. Hyperconjugative stabilization via orf/zo-Me3Si or... 

The pulsed electron beam MS technique was also used by Hiraoka and Kebarle842 to study the C4H + cations. In the ion-molecule reaction of ethane and the ethyl cation, two species were observed and identified as the 2-//-n-butoniu m cation 469 and the 2-C-w-butonium cation 470. C—C protonated ion 470 formed first rearranges to C—H protonated ion 469 (energy barrier = 9.6 kcal mol-1) and then dissociation to sec-C4H9+ + H2 takes place. 

Alkylation of methane, ethane, propane, and n-butane by the ethyl cation generated via protonation of ethylene in superacid media has been studied by Siskin,148 Sommer et al.,149 and Olah et al.150 The difficulty lies in generating in a controlled way a very energetic primary carbenium ion in the presence of excess methane and at the same time avoiding oligocondensation of ethylene itself. Siskin carried out the reaction of... 

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