Hiickel aromaticity rule

In this method, the orbital symmetry rules are related to the Hiickel aromaticity rule discussed in Chapter 2. Huckel s mle, which states that a cyclic system of electrons is aromatic (hence, stable) when it consists of 4n + 2 electrons, applies of course to molecules in their ground states. In applying the orbital symmetry principle, we are not concerned with ground states, but with transition states. In the present method, we do not examine the molecular orbitals themselves but rather the p orbitals before they overlap to form the MO. Such a set of p orbitals is called a basis set (Fig. 15.5). In investigating the possibility of a concerted reaction, we put the basis sets into the position they would occupy in the transition state. Figure 15.6 shows this for both the... 

Heterocyclics with seven and more ring members display an enormous variety of shapes. Bond lengths are often close to those of open chain counterparts, but bond angles can be greatly different. Aromaticity is possible where the conditions of planarity and Hiickel s rule are met, but the majority of fully unsaturated large heterocycles are not aromatic (see below). 

The tropylium and the cyclopropenyl cations are stabilized aromatic systems. These ions are arumatic according to Hiickel s rule, with the cyclopropeniiun ion having two n electrons and the tropyliiun ion six (see Section 9.3). Both ring systems are planar and possess cyclic conjugation, as is required for aromaticity. 

One of molecular- orbital theories early successes came in 1931 when Erich Hiickel discovered an interesting pattern in the tt orbital energy levels of benzene, cyclobutadiene, and cyclooctatetraene. By limiting his analysis to monocyclic conjugated polyenes and restricting the structures to planar- geometries, Hiickel found that whether a hydrocar bon of this type was aromatic depended on its number of tt electrons. He set forth what we now call Hiickel s rule ... 

Hiickel proposed his theory before ideas of antiaiomaticity emerged. We can fflnplify his generalization by noting that among the hydrocarbons covered by Hiickel s rule, those with (4n) tt electrons not only are not aromatic, they are antiaromatic. 

Benzene, cyclobutadiene, and cyclooctatetraene provide clear- examples of Hiickel s rule. Benzene, with six tt electrons is a (4n + 2) system and is predicted to be aromatic by the rule. Square cyclobutadiene and planar- cyclooctatetraene are 4n systems with four and eight tt electrons, respectively, and are antiarornatic. 

Section 11.19 An additional requiiement for aromaticity is that the number of tt electrons in conjugated, planar, monocyclic species must be equal to An + 2, where n is an integer. This is called Hiickel s rule. Benzene, with six TT electrons, satisfies Hiickel s rule for n =. Square cyclobutadiene (four TT electrons) and planar- cyclooctatetraene (eight tt electrons) do not. Both are examples of systems with An tt electrons and are antiaromatic. 

Hiickel s rule states that planar cyclic 71 systems involving 4n+2 electrons will be unusually stable ( aromatic ), while cyclic 7i systems with 4n electrons will be unstable ( antiaromatic ). 

Draw an energy diagram for the three molecular orbitals of the cyclopropenyl system (C l I3). How ate these three molecular orbitals occupied in the cyclopropenyl anion, cation, and radical Which of the three substances is aromatic according to Hiickel s rule ... 

Thiepin, as a seven-membered conjugated system with sulfur as heteroatom, is a member of the 8 7t-electron heteroannulenes which are antiaroinatic according to Hiickel s rule. In contrast to oxepin, thiepin is not stable at room temperature and no valence isomerism with an arene sulfide has been observed. Stable thiepins are obtained only when two bulky substituents, e.g. /ert-butyl, are introduced into positions 2 and 7. In benzothiepins the annellation effect of the aromatic rings contributes decisively to the stability of these compounds stability increases with an increasing number of fused benzene rings. 

Although [34]octaphyrin 80 fulfills Hiickel s rule, the II NMR spectrum indicates by the high-field shift of the methine protons that the system is nonaromatic. The X-ray structure analysis demonstrates clearly the reason for the lack of aromatic stabilization, namely the nonplanar loop conformation in which the whole macrocycle is twisted similarly to the [32]octaphyrin structure and which is also found for [36]octaphyrin and [40]decaphyrin structures (vide infra). 

The most obvious compound in which to look for a closed loop of four electrons is cyclobutadiene (52). Hiickel s rule predicts no aromatic character here, since 4 is not a number of the form 4 + 2. There is a long history of attempts to prepare this... 

It is strong evidence for Hiickel s rule that 59 and 60 are not aromatic while the cyclopropenyl cation (55) and the cyclopentadienyl anion (39) are, since simple resonance theory predicts no difference between 59 and 55 or 60 and 39 (the same number of equivalent canonical forms can be drawn for 59 as for 55 and for 60 as for 39). 

In the 1930 s HiickeP proposed, on the basis of molecular-orbital calculations, a theoretical criterion for aromaticity of cyclic polyenes, known as Hiickers rule, which states that cyclic polyenes should be aromatic if, and only if, they contain 4n- -2 Jt-electrons. At that time only two of such cyclic polyenes were known benzene and cyclo-pentadienyl anion, each having six rc-electrons and satisfying Huckel s rule. Since then, the validity of Hiickel s rule had not been challenged... 

Results from X-ray studies of three annulenes are presented In Table 8. According to Hiickel s rule [14]annulene (14-ANN) and [18]annulene (18-ANN) should be aromatic and most probably planar molecules, while [16]annulene (16-ANN), as a [4n]annulene, should be antiaromatic. The [14]annulene molecule is nonplanar, with a structure that approaches C2h symmetry. The cause of the nonplanarity is the steric overcrowding in the center of the molecule. While the spread of the individual bond lengths implies possible significant differences, there is no significant pattern to the values obtained. 

In general, linear 7r-electron systems with Z1r = 2N electrons at the lowest energy levels have closed-shell singlet states while cyclic systems reach closed shell structures only when ZT = 4N + 2. Cyclic 7r-electron systems with Zn 4N + 2 will therefore exhibit multiplet ground states according to Hund s rules, and should be chemically reactive because of the unpaired electrons. Hiickel s rule that predicts pronounced stability for so-called aromatic ring systems with 4jV + 2 7r-electrons is based on this shell structure. The comparison with cyclic systems further predicts that ring closure of linear 7r-electron systems should be exothermic by an amount... 

For example, both Hiickel aromatics B and C conform to the Wade-Mingos electron counting rules [2] (see Chapter 1.1.2) and to the structural systematics developed for boranes and heteroboranes [1] the hexagonal bipyramid with the apices removed is in agreement with an arachno electron count of 18 SE for (CH)g [2],... 

A rule for helping to predict if a monocyclic planar system of delocalized tt electrons will exhibit aromatic character. The ring system will be aromatic if the number of delocalized tt electrons equals 4n -h 2 where nisa positive integer or zero. For example, the ring system in phenylalanine obeys Hiickel s rule. See Aromaticity... 

Hiickel s rule (1931) for planar species states that if the number of ir electrons is equal to 2 + 4n, where n equals zero or a whole number, the species is aromatic. The rule was first applied to carbon-containing monocyclics in which each C is capable of being 5p -hybridized to provide a p orbital for extended v bonding it has been extended to unsaturated heterocyclic compounds and fused-ring compounds. Note that benzene corresponds to n = 1. 

Aromaticity is observed when all bonding MO s are filled and nonbonding MO s, if present, are empty or completely filled. Hiickel s rule arises from this requirement. A species is antiaromatic if it has electrons in antibonding MO s or if it has half-filled bonding or nonbonding MO s, provided it is planar. 

An aromatic compound has a molecular structure containing cyclic clouds of delocalized tt electrons above and below the plane of the molecule, and the TT clouds contain a total of 4n -f 2) tt electrons (where n is a whole number). This is known as Hiickel s rule (introduced first by Erich Hiickel in 1931). Eor example, benzene is an aromatic compound. 

If n = 1, we have 4 x 1+2 = 6, which means that any compound containing a total number of six tt electrons is an aromatic compound. In the above structure of benzene, there are three double bonds and six tt electrons, and it is a planar molecule. Thus, benzene follows Hiickel s rule, and is an aromatic compound. 

Heterocyclic These are compounds having at least one hetero atom (any other atom but carbon, e.g. O, N and S) within the ring, and conforming to Hiickel s rule. The aromaticity of heterocyclic compounds, e.g. pyridine and pyrrole, can be explained as follows. 

Hiickel s rule, based on molecular-orbital calculations,123 predicts that electron rings will constitute an aromatic system only if the number of electrons in the ring is of the form... 

The most obvious compound in which to look for a closed loop of four electrons is cyclobutadiene (44).135 Hiickel s rule predicts no aromatic character here, since 4 is not a number of the form 4n + 2. There is a long history of attempts to prepare this compound and its simple derivatives, and, as we shall see, the evidence fully bears out Hiickel s prediction— cyclobutadienes display none of the characteristics that would lead us to call them aromatic. More surprisingly, there is evidence that a closed loop of four electrons is actually ami-aromatic.1 If such compounds simply lacked aromaticity, we would expect them to be about as stable as similar nonaromatic compounds, but both theory and experiment show that they are much less stable.137 An antiaromatic compound may be defined as a compound that is destabilized by a closed loop of electrons. 

For large rings, aromaticity is possible where the conditions of planarity and Hiickel s rule are met, but the majority of fully unsaturated large heterocycles are not aromatic. 

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