Cycloheptatriene cation

Aromatic cyclic ions cyclopentadiene anion, cycloheptatriene cation (6 electrons)... 

Simonetta and Heilbronner (1964) recently carried out calculations by the valence bond (VB) method for some simple cations, and compared the results obtained by this method, inter alia, with the results of Colpa and collaborators (1963) and of Koutecky and Paldus (1963). In the case of the proton addition complexes of mesitylene and cyclohepta-triene, the electron excitation energies calculated by the VB method agree very well with experiments, and also agree to a good approximation with the results of Cl calculations. The calculations also successfully reproduce the electron density of the cycloheptatriene cation. In this, a perturbation calculation allowed for the AO s adjoining the —CHg—CH2-lihkage. 

As to the cation-radical version of this isomerization, there are testimonies on the transition of the norcaradiene carcass into the cycloheptatriene skeleton. Calculations at the B3LYP level shows that cycloheptatriene cation-radical is more stable than norcaradiene cation-radical by ca. 29 kJ mol (Norberg et al. 2006). Hydrocarbon ion-radicals with strained ring structures have a tendency to undergo facile rearrangement to enforce the unpaired electron delocalization and release their strain energy. 

Resonance, as introduced in Chapter 2, explains stability of anions and rationalizes trends in pKa values. However, resonance can also be used to rationalize the stability of cations (positively charged ions). As shown in Scheme 4.7, the stability of the cyclohepta-triene cation is explained by its resonance forms. There is, of course, another reason for the stability of the cycloheptatriene cation, which relates to the principles of aromaticity and which will not be discussed in detail in this book. 

In some cases, a resonance structure is required to see an aromatic system. The increased stability associated with an aromatic system is found for the structure, although the compounds do not appear aromatic unless the resonance structure is considered. Azulene, which can be drawn as a cyclopentadienyl anion fused to a cycloheptatriene cation, and cyclopropenone, which can be written as possessing a cyclopropenyl cation, are two examples (see margin). 

If triphenylmethyl chloride in ether is treated with sodium, a yellow colour is produced due to the presence of the anionic spiecies PhsC". Alternatively, if triphenylmethyl chloride is treated with silver perchlorate in a solvent such as THF, the triphenylmethyl cation is obtained. More conveniently, triphenylmethyl salts, PhsC X", can be obtained as orange-red crystalline solids from the action of the appropriate strong acid on triphenylcarbinol in ethanoic or propanoic anhydride solution. The perchlorate, fluoroborate and hexafluoro-phosphate salts are most commonly used for hydride ion abstraction from organic compounds (e.g. cycloheptatriene gives tropylium salts). The salts are rather easily hydrolysed to triphenylcarbinol. 

When we say cycloheptatriene is not aromatic but cycloheptatrienyl cation is we are not comparing the stability of the two to each other Cycloheptatriene is a stable hydrocarbon but does not possess the special stability required to be called aromatic Cycloheptatrienyl cation although aromatic is still a carbocation and reasonably reac tive toward nucleophiles Its special stability does not imply a rock like passivity but rather a much greater ease of formation than expected on the basis of the Lewis struc ture drawn for it A number of observations indicate that cycloheptatrienyl cation is far more stable than most other carbocations To emphasize its aromatic nature chemists often write the structure of cycloheptatrienyl cation m the Robinson circle m a ring style... 

The Hiickel rule predicts aromaticity for the six-7c-electron cation derived from cycloheptatriene by hydride abstraction and antiaromaticity for the planar eight-rc-electron anion that would be formed by deprotonation. The cation is indeed very stable, with a P Cr+ of -1-4.7. ° Salts containing the cation can be isolated as a product of a variety of preparative procedures. On the other hand, the pK of cycloheptatriene has been estimated at 36. ° This value is similar to those of normal 1,4-dienes and does not indicate strong destabilization. Thus, the seven-membered eight-rc-electron anion is probably nonplanar. This would be similar to the situation in the nonplanar eight-rc-electron hydrocarbon, cyclooctatetraene. 

Both the cycioheptatrienyl radical and the anion are reactive and difficult to prepare. The six-Tr-electron cation, however, is extraordinarily stable. In fact, the cycioheptatrienyl cation was first prepared more than a century ago by reaction of Br2 with cycloheptatriene (Figure 15.7), although its structure was not recognized at the time. 

Figure 15.7 Reaction of cycloheptatriene with bromine yields cycloheptatrienylium bromide, an ionic substance containing the cycioheptatrienyl cation. The electrostatic potential map shows that all seven carbon atoms are equally charged and electron-poor blue).

The facile thermal isomerization (17) of norbornadiene derivatives [71]-[77] to cycloheptatrienes in polar solvents has been explained in terms of the initial heterolytic cleavage of the strained C(l)-C(7) bond (Hoffmann and Hauser, 1965 Lemal et al., 1966 Hoffmann, 1971, 1985 Lustgarten and Richey, 1974 Hoffmann et al., 1986 Bleasdale and Jones, 1993). The resulting zwitterion intermediates are stabilized by the cation-stabilizing groups attached to C(7) and the cyclohexadienyl-type delocalization of the negative charge. 

More recent work on the chemistry of gaseous 1,3,5-cycloheptatriene radical cations concerns the energetics and dynamics of the interconversion with ionized toluene and the competing losses of H from both isomers. Lifshitz and coworkers22,143 have reported on the details of the energy surface of the ions. Most importantly, the critical energies... 

Formation of dihydrotropylium ions is a key feature of the C H9+ hypersurface. Currently, efforts in our laboratory276 have concentrated on the presence of different C H9+ isomers by probing their bimolecular reactivity. Thus, gas-phase titration in the FT-ICR mass spectrometer has revealed that mixtures of C7H9+ ions are formed by protonation of 1,3,5-cycloheptatriene, 6-methylfulvene and norbomadiene as the neutral precursors but that, in contrast to the results obtained by CS mass spectrometry, fragmentation of the radical cations of limonene yields almost exclusively toluenium ions275. 

The photo-oxidation of the aryl-substituted cycloheptatrienes 7-(/ -methoxy-phenyl)cycloheptatriene and 7-, 1- and 3-(/ -dimethylaminophenyl)cycloheptatrienes to the corresponding radical cations in de-aerated acetonitrile solution was accomplished by electron transfer to the electronically excited acceptors 9,10-dicyanoanthracene, iV-methylquinolinium perchlorate, iV-methylacridinium perchlorate and l,T-dimethyl-4,4-bipyridinium dichloride. In the case of l- p-methoxyphenyl)cycloheptatriene (62), deprotonation of the radical cation occurs successfully, compared with back electron transfer, to give a cycloheptatrienyl radical (63) which undergoes a self-reaction forming a bitropyl. If the photooxidation is done in air-saturated acetonitrile solution containing HBF4 and one of the acceptors, the tropylium cation is formed. Back electron transfer dominates in the / -dimethylaminocycloheptatrienes and the formation of the cycloheptatrienyl radical is prevented. 

The tropylium cation (274) first observed 1891 and rediscovered in 1957 is perfectly stable and isolable. Cyclopropenyl cations have been observed in solution a long time ago, but 273 remained elusive until very recently. Benzocyclo-propene (1) reacts with triphenylfluoroborate via hydride transfer some 5 times less rapidly than cycloheptatriene. The reaction of deuterated 1 exhibits a kinetic isotope effect of 7.0. However, only a low yield of benzaldehyde (277), the expected hydrolysis product of 273, could be isolated from the reaction mixture. ... 

The MP2/4-31G/STO-3G calculations show (83TL1863) the tropylium cation to be 112.7 kcal/mol more stable than the hypothetical bicyclo [4.1.0]hepta-2,4-dien-7-yl cation. This difference, attributed to the effects of aromatic stabilization, should be compared with the value of AE (172) - (124) = 44.8 kcal/mol (at the same computational level). Therefore, the energy of aromatic stabilization of borepin comes to about 40% of that of the tropylium cation. The 6-31G /6-31G calculated AE (172) -(124) = 37.6 kcal/mol, whereas nonaromatic cycloheptatriene is a mere... 

Problem 10.6 Account for aromaticity observed in (o) 1,3-cyclopentadienyl anion but not 1,3-cyclopen-tadiene (b) 1,3,5-cycloheptatrienyl cation but not 1,3,5-cycloheptatriene (c) cyclopropenyl cation (d) the heterocycles pyrrole, furan and pyridine. 

Azulene can be written as fused cyclopentadiene and cycloheptatriene rings, neither of which alone is aromatic. However, some of its resonance structures have a fused cyclopentadienyl anion and cycloheptatrienyl cation, which accounts for its aromaticity and its dipole moment of 1.0 D. 

Cyclodecyl cation hydride bridge, 147 1,4-Cycloheptadiene, 170, 171 Cycloheptatriene, 281 Cycloheptatrienes rearrangements, 290 Cycloheptatrienylidene, 275 interaction diagram, 276... 

Although the structural elements supporting cyclopropyl homoaromaticity and nobond homoaromaticity are now generally understood, it is not clear under what conditions a homoconjugated molecule will prefer to occupy a single minimum or to adopt classical forms connected by a valence tautomeric equilibrium. Of course, one can explain that the norcaradiene/cycloheptatriene system is characterized by a valence tautomeric equilibrium while the homotropenylium cation possesses a single minimum PES. This has simply... 

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