Cyclooctatetraene dication

Cyclooctatetraene dications 225407 4m and benzocyclobutadiene dications 226471 472 are well studied. The parent cyclooctatetraene dication is still elusive, despite repeated attempts to prepare it under a variety of superacid conditions. 

Electrolytic reduction of 4-cyclooctenone leads smoothly in 64 % yield to cis-bicyclo[3.3.0]octan-l-ol.106) The thermolysis of octachlorocyclooctatetraene produces perchlorinated bicyclo[3.3.0]octatrienes,107,108) several of which have been examined in detail by X-ray structural methods.109) The 1,3,5,7-tetramethyl-cyclooctatetraene dication (57), generated by oxidation of the neutral hydrocarbon with antimony pentafluoride in S02C1F at —78 °C and below, is subject to dis-rotatory cyclization above — 60°.1 °) The latter step does not follow orbital sym-... 

It suggests that it is not the size of the ring but the number of electrons present in it determines whether a molecule would be aromatic or antiaromatic. In fact the molecules with An+ 2) n electrons are aromatic whereas with (An, 0) n electrons are antiaromatic. Thus, benzene, cyclopropenyl cation, cyclobutadiene dication (or dianion), cyclopentadie-nyl anion, tropylium ion, cyclooctatetraene dication (or dianion), etc. possess (4 + 2) ti electrons and hence aromatic whereas cyclobutadiene, cyclopentadienyl cation, cycloheptatrienyl anion, cyclooctatetraene (non-planar) etc. have An n electrons which make them antiaromatic . Systems like [10] annulene are forced to adopt a nonplanar conformation due to transannular interaction between two hydrogen atoms and hence their aromaticity gets reduced even if they have (An + 2)n electrons. On the other hand the steric constraints in systems like cyclooctatetraene force it to adopt a tube-like non-planar conformation which in turn reduces its antiaromaticity. Various derivatives of benzene like phenol, toluene, aniline, nitrobenzene etc. are also aromatic where the benzene ring and the n sextet are preserved. In homoaromatic " systems, like cyclooctatrienyl cation, delocalization does not extend over the whole molecule. 

Our success in super-stabilization of cation 6 led us to the preparation of a higher homologue, that is, cyclooctatetraene (COT), fully annelated with BCO units 9 (9). As compared with a large number of studies on its radical anion or dianions, the studies on the cationic species of COT have been quite limited. There have been only one study by Olah and Paquette on the substituted COT dication (70), which is a typical 6n Hiickel aromatic system, and few sporadic studies on radical cations, which involve indirect spectral observations, such as electronic spectra in Freon matrix at low temperature (77,72) and constant-flow ESR study (13). 

Problem 10.30 Design a table showing the structure, number of tt electrons, energy levels of tt MO s and electron distribution, and state of aromaticity of (a) cyclopropienyl cation, b) cyclopropenyl anion, (c) cyclobutadiene, (d) cyclobutadienyl dication, (c) cyclopentadienyl anion, (/) cyclopentadienyl cation, (g) benzene, (h) cycloheptatrienyl anion, (/) cyclooctatetraene, (/ ) cyclooctatetraenyl dianion. ... 

There is, however, nmr evidence that indicates that the tub form is in rapid equilibrium with a very small amount of the planar form at room temperature. There is about a 15-kcal mole-1 energy difference between the two forms. The dication, C8HS2 , and the dianion of cyclooctatetraene, C8HR2e, which have (4 n + 2)tt electrons, appear to exist in planar conformations (see Exercise 21-16, p. 996). 

The dication adopts a three-legged piano-stool configuration in which the O-U-O angles vary from 84.0° to 88.2° with a mean value of 87(3)°, and average COT-U-O angles of 127(1)°. The uranium atom is 1.92(2) A away from the planar cyclooctatetraene ring, and the mean U-G bond distance is 2.65(3) A. These values compare well with those determined in the monocationic cyclooctatetraene complexes [(COT)U(NEt2)(THF)3]+.161... 

Addition of two electrons to cyclooctatetraene would lead to a 10ji-electron system, the cyclooctatetraenyl dianion, Cyclooctatetraene, which is non-planar, reacts with potassium in tetrahydrofuran to give dipotassium cyclooctatetraenide, which is planar. The C-C bond lengths are all the same (141 pm). At low temperatures, a dication is formed when cyclooctatetraene reacts with SbF.. This also has some aromatic characteristics in keeping with a 6jt-electron system. 

Thus the stabilization energy calculation agrees with the deduction from the disposition of filled MOs (i.e. with the 4n + 2 rule) that the cyclobutadiene dication should be stabilized by electron delocalization, which is in some agreement with experiment [45], More sophisticated calculations indicate that cyclic 4n systems like cyclobutadiene (where planar cyclooctatetraene, for example, is buckled by steric factors and is simply an ordinary polyene) are actually destabilized by n electronic effects their resonance energy is not just zero, as predicted by the SHM, but less than zero. Such systems are antiaromatic [17,46],... 

In 1945 Michael J. S. Dewar suggested that the tropylium ion (the cation derived from cycloheptatriene) should also be aromatic (Figure 9). This was confirmed in 1954 since then, the dianion of butadiene and the dication of cyclooctatetraene have also been shown to be aromatic. Like benzene, all four of these ions are planar rings with six tt electrons. According to Hiickel s rule the cyclopropene cation should also exhibit aromaticity, and it does. (In this case n = 0, and 4n + 2 = 2.) The planar anion of cyclononatetraene and the dianion of cyclooctatetraene should also be aromatic (n = 2, and 4n + 2 = 10), and both of them are. 

It is difficult to choose a reference compound against which to judge the stability of the dication. That it can be formed at all, however, is suggestive of special stabilization associated with the two TT-electron system. The dianion formed by adding two electrons to the TT system of cyclobutadiene also meets the 4 - -2 criterion. In this case, however, four of the six electrons would occupy HMO nonbonding orbitals, so high reactivity could be expected. There is some evidence that this species may have a finite existence. " Reaction of 3,4-dichlorocyclobutene with sodium naphthalenide, followed a few minutes later by methanol-0-<7 gives a low yield of 3,4-di-deutero-cyclobutene. The inference is that the dianion [ 4114 ] is present, but there has not yet been direct experimental observation of this species. Cyclooctatetraene is reduced by alkali metals to a dianion. 

It is also possible to add electrons to cyclooctatetraene by treating it with alkali metals and a dianion results. X-ray structures reveal this dianion to be planar, again with all C-C bond lengths the same (140.7 pm). The difference between the anion and cation of cyclooctatetraene on the one hand and cyclooctatetraene on the other is the number of electrons in the 7c system. Neutral, non-planar, cyclooctatetraene has eight jc electrons, the planar dication has six 7c electrons (as does benzene), and the planar anion has ten. 

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