Aromaticity *Aromaticity can be defined as the ability to sustain an induced ring current.

A compound with this ability is called diatropic. *There are several methods of determining whether a compound can sustain a ring current, but the most important one is based on NMR chemical shifts. Thus ordinary alkene hydrogens are found at ~ 56 , while the hydrogens of benzene rings are located at ~ 78 . If the protons attached to the ring are shifted downfield from the normal alkene region, we can conclude that the molecule is diatropic, and hence aromatic. In addition, if the compound has protons above or within the ring, then if the compound is diatropic, these will be shifted upfield. One drawback to this method is that it cannot be applied to compounds that have no protons in either category, for example, the dianion of squaric acid . Unfortunately, 13C NMR is of no help here, since these spectra do not show ring currents. *For a molecule to exhibit aromaticity 1. The molecule must be cyclic, planar with uninterrupted cloud of electrons above and below the plane of the ring. 2. It should have 4n+2 electrons. *Antiaromatic systems exhibit a paramagnetic ring current, which causes protons on the outside of the ring to be shifted upfield while any inner protons are shifted downfield. Compounds that sustain a paramagnetic ring current are called paratropic. *Anti aromaticity is maximum if compound is planar and bond lengths are equal. Molecules show a tendancy to distort from planarity inorder to reduce anti aromaticity. *For a molecule to exhibit anti aromaticity 1. The molecule must be cyclic, planar with uninterrupted cloud of electrons above and below the plane of the ring. 2. It should have 4n electrons. *Antiaromatic compounds have an even number of pairs of electrons (4n, n = 1, 2, 3 etc). It should be noted that an aromatic compound is more stable compared to an analogous cyclic compound with localized electrons, where as an antiaromatic compound is less stable compared to an analogous cyclic compound with localized electrons *In 4n+2 systems delocalization increases the stability where as in 4n systems, delocalization decreases stability *Non aromatic compounds, are not aromatic due to reasons such as lack of planarity or disruption of delocalization. They may contain 4n or 4n+2 electrons. Frost Diagram The relative energies of p molecular orbitals in planar cyclic conjugated systems can be determined by a simplified approach developed by A. A. frost in 1953. This involves the following steps: 1) Draw a circle 2) Place the ring (polygon representing the compound of interest) in the circle with one of its vertices pointing down. Each point where the polygon touches the circle represents an energy level. 3) Place the correct number of electrons in the orbitals, starting with the lowest energy orbital first, in accordance with Hunds rule. If the polygon touches the circle at a horizontal diameter, that point would represent a nonbonding orbital . Energy levels below this line indicate bonding MOs and those above are anti-bonding.

Aromatic compounds will have all occupied molecular orbitals completely filled where as antiaromatic compounds would have incompletely filled orbitals. If an antiaromatic system (4n electrons) has the freedom to undergo conformational change and become nonaromatic that would do so. The antiaromatic state is less stable than aromatic and nonaromatic forms.

Cyclobutadiene or [4]-annulene 4 electrons (even number of pairs; 4n, n = 1) Cyclic, planar, uninterrupted ring of p orbital bearing atoms (conjugation) Antiaromatic Being antiaromatic, cyclobutadiene is unstable. It can be isolated only under controlled conditions such as in Argon matrix or using trapping agents such as dienes. Studies show that it has a rectangular structure rather than a square, with C-C bond length of 1.567 and C=C bond length of 1.346 .

Cyclobutadienyl dication

The fifth atom may be carbon if it has an unshared pair. Cyclopentadiene has unexpected acidic properties (pKa~15) since on loss of a proton, the resulting carbanion is greatly stabilized by resonance although it is quite reactive.The cyclopentadienide ion is usually represented as in 58. Resonance in this ion is greater

than in pyrrole, thiophene, and furan, since all five forms are equivalent. The resonance energy has been estimated to be 2427 kcal mol-1 .

Alkyl halides such as cyclopentyl chloride are nonpolar and dissolve in non-polar solvents and remain insoluble in water. Surprisingly, cycloheptatrienyl bromide is an exception. It is insoluble in nonpolar solvents, but dissolves in water! It turns out that cycloheptatrienyl bromide is an ionic compound, since its cation (known as tropylium cation) is aromatic. In the covalent form, there is no continuity in p orbital overlap as one of the carbon atoms is sp3 hybridized. Another seven-membered ring that shows some aromatic character is tropone. The tropylium ion has an aromatic sextet spread over seven carbon atoms. An analogous ion, with the sextet spread over eight carbon atoms, is 1,3,5,7- tetramethylcyclooctatetraene dictation . This ion is diatropic and approximately planar.

Aromaticity in higher Annulenes Completely conjugated monocyclic hydrocarbons are called annulenes.

In [10]-annulene, there is considerable steric interaction between hydrogens at 1 and 6 positions. Further, a planar form (regular decagon) requires an angle of 144o between carbon atoms which is too large to accommodate in a sp2 framework. The system prefers a nonplanar conformation and is not aromatic. Bridging C1 and C6 in [10]-annulene leads to the compound VII which is reasonably planar with all the bond distances in the range of 1.37-1.42Ao and show aromaticity (In NMR, outer protons are found at 6.97.3 and the bridgehead methylene at -5.0 ).

[12]-annulene [12]-annulene (4n, n = 3) is antiaromatic and hence is not stable above -50oC. Its dianion (4n+2, n = 3) is however stable up to 30oC and is aromatic

[14]-annulene Bond lengths in [14]-annulene range from 1.35-1.41Ao but do not show the alternating pattern of localized polyenes. It is aromatic (except for the isomers that are not planar). NMR shows that it is in conformational equilibrium as shown below. The steric interactions associated with internal hydrogens can be minimized if C3, C6, C10 and C13 positions are locked using suitable bridging units. Thus trans-15,16dimethyldihydropyrene and its diethyl and dipropyl homologs are aromatic with C-C bond distances between 1.39-1.40 Ao. Conformational flexibility in [14]-annulene can be restricted by inserting triple bond in place of one of the more double bonds. Here, the triple bond contributes only two electrons for delocalization leaving the other two localized.

[16]-annulene [16]-annulene shows significant bond alteration, characteristic of a polyene structure (C-C, 1.46Ao; C=C, 1.34 Ao). It is nonplanar and is nonaromatic. Its dianion has been prepared and shows aromatic character (4n+2 system).

[18]-annulene The cavity in [18]-annulene is sufficiently large and hence the steric interaction involving internal hydrogens is at minimum. The molecule is free of any significant angle strain, nearly planar, and show aromaticity. Its estimated resonance energy is 37 kcal/mol, which is in the range as that of benzene. The planarity and extent of delocalization in [18]-annulene can be improved by constructing its periphery around a saturated core as in VIII (Figure 13). This compound shows significantly improved delocalization and aromaticity (2 times) compared to [18]-annulene.

Heterocycles The heterocyclic compounds pyrrole, thiophene, and furan are the most important examples of this kind of aromaticity, although furan has a lower degree of aromaticity than the other two. Resonance energies for these three compounds are, respectively, 21, 29, and 16 kcal mol-1. Order of aromaticity T > P > F (electronegativity S-2.5, N-3.0, O-3.5).

Aromaticity of fused aromatic system *For benzene, naphthalene, anthracene, and phenanthrene, for which we can draw, respectively, two, three, four, and five principal canonical forms, the resonance energies are, respectively, 36, 61, 84, and 92 kcal mol-1.

As the number of aromatic rings increases, the resonance energy per electron decreases. As a result, larger polynuclear aromatic hydrocarbons have a tendency to undergo addition reaction to an internal ring to give more stable compounds.

Azulene (intensely blue colored solid) is one of the few nonbenzenoids that appears to have significant aromatic stabilization. It has a dipole moment (0.8 D). It acts like a combination of cyclopentadienyl anion and cycloheptatrienyl cation by transferring 1e- from heptagon to pentagon. Azulene readily undergoes aromatic substitution at pentadienyl ring. In contrast, Pentalene and heptalene which posses fused five and seven membered rings respectively are not stable as expected on the grounds of antiaromaticity. Attempted synthesis of the former led to the formation of a dimmer, where as the latter undergo polymerization. It is interesting to note that the conjugate acid of heptalene is very stable, reflecting the stability of resulting Tropylium cation. *Not all fused systems can be fully aromatic. Thus for phenalene there is no way double bonds can be distributed so that each carbon has one single and one double bond. However, phenalene is acidic and reacts with potassium methoxide to give the corresponding anion , which is completely aromatic. So are the corresponding radical and cation, in which the resonance energies are the same.

*For triphenylene, there are eight canonical forms like I, in which none of the three bonds marked a is a double bond and only one form II in which at least one of them is double. Thus the molecule behaves as if the 18 electrons were distributed so as to give each of the outer rings a sextet, while the middle ring is empty. Since none of the outer rings need share any electrons with an adjacent ring, they are as stable as benzene; triphenylene, unlike most fused aromatic hydrocarbons, does not dissolve in concentrated sulfuric acid and has a low reactivity. This phenomenon, whereby some rings in fused systems give up part of their aromaticity to adjacent rings, is called annellation and can be demonstrated by UV spectra.

Fulvalenes - Among possible symmetrical structures, pentafulvalene and heptafulvalene have been prepared, but were found to exhibit polyene character. However, when a combination of rings, such as cyclopentadiene and cyclopropene were examined, results were in support of the existence of dipolar resonance structures. The large measured dipole moments of phenyl substituted analog x and reduced barrier of rotation (as revealed by NMR) of the dialkyl substituted analog x are manifestations of such effects.

Metallocenes The carbon iron bonding in Ferrocene may be looked upon as a result from overlap between the inner lobes of the p orbital of the cyclopentadienyl anions and 3d orbital of the iron atoms. A noteworthy feature of many organic derivatives of transition metals is that the organic group is bonded to the metal through the p system rather than by a sbond as in (benzene/tricarbonyl chromium).

Homoaromaticity If a stabilized cyclic conjugated system (4n+2 e s) can be formed by bypassing one saturated atom(sp 3 carbon atom), that lead to homoaromaticity. Compared to true aromatic systems, the net stabilization here may be low due to poorer overlap of orbitals. Cyclooctatrienyl cation (homotropylium ion) formed when cyclooctatetraene is dissolved in concentrated sulfuric acid is the best example to demonstrate homoaromaticity. Here, six electrons are spread over seven carbon atoms as in Tropylium cation.

Annulenes-summary

Monocyclic, completely conjugated polyenes. According to the HMO, the 4n+2=2,6,10,14-electron annulenes are aromatic, while the 4n=4,8,12,16-electron annulenes are anti-aromatic.

Fullerenes (Bucky balls and bowels) Fullenes are spherical conjugated polyenes that display aromatic properties. These recently discovered forms of carbon are related to bowl-shaped aromatic hydrocarbons whose parent is the bowl-shaped hydrocarbon corannulene. If aromatic systems are constructed of a two-dimensional array of fused six-membered rings, a planar aromatic system results that upon its ultimate extension is called graphite. On the other hand, if the aromatic system is constructed five- and six-membered rings where every fivemembered ring is isolated from other fivemembered rings by circles of six-membered rings, then a curved aromatic surface results. Upon ultimate extension, this pattern of construction results in carbon nanotubes and fullerenes.