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Two different resonance forms of benzene (top) combine to produce an average structure (bottom) In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected by the stabilization of conjugation alone. The earliest use of the term was in an article by August Wilhelm Hofmann in 1855.[1] There is no general relationship between aromaticity as a chemical property and the olfactory properties of such compounds. Aromaticity can also be considered a manifestation of cyclic delocalization and of resonance.[2][3][4] This is usually considered to be because electrons are free to cycle around circular arrangements of atoms that are alternately single- and double-bonded to one another. These bonds may be seen as a hybrid of a single bond and a double bond, each bond in the ring identical to every other. This commonly seen model of aromatic rings, namely the idea that benzene was formed from a six-membered carbon ring with alternating single and double bonds (cyclohexatriene), was developed by Kekul (see History section below). The model for benzene consists of two resonance forms, which corresponds to the double and single bonds superimposing to give rise to six one-and-a-half bonds. Benzene is a more stable molecule than would be expected without accounting for charge delocalization.
Theory
As is standard for resonance diagrams, a double-headed arrow is used to indicate that the two structures are not distinct entities, but merely hypothetical possibilities. Neither is an accurate representation of the actual compound, which is best represented by a hybrid (average) of these structures, which can be seen at right. A C=C bond is shorter than a CC bond, but benzene is perfectly hexagonalall six carbon-carbon bonds have the same length, intermediate between that of a single and that of a double bond. A better representation is that of the circular bond (Armstrong's inner cycle), in which the electron density is evenly distributed through a -bond above and below the ring. This model more correctly represents the location of electron density within the aromatic ring. The single bonds are formed with electrons in line between the carbon nuclei these are called -bonds. Double bonds consist of a -bond and a -bond. The -bonds are formed from overlap of atomic p-orbitals above and below the plane of the ring. The following diagram shows the positions of these p-orbitals:
Since they are out of the plane of the atoms, these orbitals can interact with each other freely, and become delocalized. This means that, instead of being tied to one atom of carbon, each electron is shared by all six in the ring. Thus, there are not enough electrons to form double bonds on all the carbon atoms, but the "extra" electrons strengthen all of the bonds on the ring equally. The resulting molecular orbital has symmetry.
The delocalized picture of benzene (and other aromatic compounds) has been contested by Cooper, Gerratt and Raimondi in their article published in 1986 in the journal Nature. They showed that the electrons in benzene are almost certainly localized, and the aromatic properties
of benzene originate from spin coupling rather than electron delocalization.[5] This view has been supported in the next-year Nature issue,[6][7][8] but it has been slow to permeate the general chemistry community.
History
Historic benzene formulae as proposed by Kekul.[9] The first known use of the word "aromatic" as a chemical term namely, to apply to compounds that contain the phenyl radical occurs in an article by August Wilhelm Hofmann in 1855.[1] If this is indeed the earliest introduction of the term, it is curious that Hofmann says nothing about why he introduced an adjective indicating olfactory character to apply to a group of chemical substances only some of which have notable aromas. Also, many of the most odoriferous organic substances known are terpenes, which are not aromatic in the chemical sense. But terpenes and benzenoid substances do have a chemical characteristic in common, namely higher unsaturation indices than many aliphatic compounds, and Hofmann may not have been making a distinction between the two categories. The cyclohexatriene structure for benzene was first proposed by August Kekul in 1865. Over the next few decades, most chemists readily accepted this structure, since it accounted for most of the known isomeric relationships of aromatic chemistry. However, it was always puzzling that this purportedly highly unsaturated molecule was so unreactive toward addition reactions. The discoverer of the electron J. J. Thomson, between 1897 and 1906 placed three equivalent electrons between each carbon atom in benzene. An explanation for the exceptional stability of benzene is conventionally attributed to Sir Robert Robinson, who was apparently the first (in 1925)[10] to coin the term aromatic sextet as a group of six electrons that resists disruption. In fact, this concept can be traced further back, via Ernest Crocker in 1922,[11] to Henry Edward Armstrong, who in 1890, in an article entitled The structure of cycloid hydrocarbons, wrote the (six) centric affinities act within a cycle...benzene may be represented by a double ring (sic) ... and when an additive compound is formed, the inner cycle of affinity suffers disruption, the contiguous carbon-atoms to which nothing has been attached of necessity acquire the ethylenic condition.[12] Here, Armstrong is describing at least four modern concepts. First, his "affinity" is better known nowadays as the electron, which was to be discovered only seven years later by J. J. Thomson. Second, he is describing electrophilic aromatic substitution, proceeding (third) through a
Wheland intermediate, in which (fourth) the conjugation of the ring is broken. He introduced the symbol C centered on the ring as a shorthand for the inner cycle, thus anticipating Eric Clar's notation. It is argued that he also anticipated the nature of wave mechanics, since he recognized that his affinities had direction, not merely being point particles, and collectively having a distribution that could be altered by introducing substituents onto the benzene ring (much as the distribution of the electric charge in a body is altered by bringing it near to another body). The quantum mechanical origins of this stability, or aromaticity, were first modelled by Hckel in 1931. He was the first to separate the bonding electrons into sigma and pi electrons.
Aromatic molecules are able to interact with each other in so-called - stacking: The systems form two parallel rings overlap in a "face-to-face" orientation. Aromatic molecules are also able to interact with each other in an "edge-to-face" orientation: The slight positive charge of the substituents on the ring atoms of one molecule are attracted to the slight negative charge of the aromatic system on another molecule. Planar monocyclic molecules containing 4n electrons are called antiaromatic and are, in general, destabilized. Molecules that could be antiaromatic will tend to alter their electronic or conformational structure to avoid this situation, thereby becoming non-aromatic. For example, cyclooctatetraene (COT) distorts itself out of planarity, breaking overlap between adjacent double bonds. Relatively recently, cyclobutadiene was discovered to adopt an asymmetric, rectangular configuration in which single and double bonds indeed alternate; there is no resonance and the single bonds are markedly longer than the double bonds, reducing unfavorable p-orbital overlap. This reduction of symmetry lifts the degeneracy of the two formerly nonbonding molecular orbitals, which by Hund's rule forces the two unpaired electrons into a new, weakly bonding orbital (and also creates a weakly antibonding orbital). Hence, cyclobutadiene is non-aromatic; the strain of the asymmetric configuration outweighs the anti-aromatic destabilization that would afflict the symmetric, square configuration.
Neutral homocyclics
Benzene, as well as most other annulenes (cyclodecapentaene excepted) with the formula CnHn where n is an even number, such as cyclotetradecaheptaene.
Heterocyclics
In heterocyclic aromatics (heteroaromats), one or more of the atoms in the aromatic ring is of an element other than carbon. This can lessen the ring's aromaticity, and thus (as in the case of furan) increase its reactivity. Other examples include pyridine, pyrazine, imidazole, pyrazole, oxazole, thiophene, and their benzannulated analogs (benzimidazole, for example).
Polycyclics
Polycyclic aromatic hydrocarbons are molecules containing two or more simple aromatic rings fused together by sharing two neighboring carbon atoms (see also simple aromatic rings). Examples are naphthalene, anthracene, and phenanthrene.
Substituted aromatics
Many chemical compounds are aromatic rings with other functional groups attached. Examples include trinitrotoluene (TNT), acetylsalicylic acid (aspirin), paracetamol, and the nucleotides of DNA.
corresponding to the paradromic topologies were first suggested by Johann Listing.[17] In carbobenzene the ring bonds are extended with alkyne and allene groups.
References
1. ^ a b A. W. Hofmann (1855). "On Insolinic Acid". Proceedings of the Royal Society 8: 1 3. doi:10.1098/rspl.1856.0002. 2. ^ Schleyer, Paul von Ragu (2001). "Introduction: Aromaticity". Chemical Reviews 101 (5): 11158. doi:10.1021/cr0103221. PMID 11749368. 3. ^ A. T. Balaban, P. v. R. Schleyer and H. S. Rzepa (2005). "Crocker, Not Armit and Robinson, Begat the Six Aromatic Electrons". Chemical Reviews 105 (10): 34363447. doi:10.1021/cr0300946. 4. ^ Schleyer, Paul von Ragu (2005). "Introduction: DelocalizationPi and Sigma". Chemical Reviews 105 (10): 3433. doi:10.1021/cr030095y. 5. ^ Cooper, David L.; Gerratt, Joseph; Raimondi, Mario (1986). "The electronic structure of the benzene molecule". Nature 323 (6090): 699. doi:10.1038/323699a0. 6. ^ Pauling, Linus (1987). "Electronic structure of the benzene molecule". Nature 325 (6103): 396. doi:10.1038/325396d0. 7. ^ Messmer, Richard P.; Schultz, Peter A. (1987). "The electronic structure of the benzene molecule". Nature 329 (6139): 492. doi:10.1038/329492a0. 8. ^ Harcourt, Richard D. (1987). "The electronic structure of the benzene molecule". Nature 329 (6139): 491. doi:10.1038/329491b0. 9. ^ August Kekul (1872). "Ueber einige Condensationsproducte des Aldehyds". Liebigs Ann. Chem. 162 (1): 77124. doi:10.1002/jlac.18721620110. 10. ^ Armit, James Wilson; Robinson, Robert (1925). "CCXI.?Polynuclear heterocyclic aromatic types. Part II. Some anhydronium bases". Journal of the Chemical Society, Transactions 127: 1604. doi:10.1039/CT9252701604. 11. ^ Ernest C. Crocker (1922). "Application Of The Octet Theory To Single-Ring Aromatic Compounds". J. Am. Chem. Soc. 44 (8): 16181630. doi:10.1021/ja01429a002. 12. ^ Henry Edward Armstrong (1890). "The structure of cycloid hydrocarbon". Proceedings of the Chemical Society (London) 6 (85): 95106. doi:10.1039/PL8900600095. 13. ^ Merino, Gabriel; Heine, Thomas; Seifert, Gotthard (2004). "The Induced Magnetic Field in Cyclic Molecules". Chemistry A European Journal 10 (17): 4367. doi:10.1002/chem.200400457. 14. ^ Alexander Kuhn, Puravankara Sreeraj, Rainer Pttgen, Hans-Dieter Wiemhfer, Martin Wilkening,Paul Heitjans (2011). "Li NMR Spectroscopy on Crystalline Li12Si7: Experimental Evidence for the Aromaticity of the Planar Cyclopentadienyl-Analogous Si56 Rings". Angew. Chem. Int. Ed. 50 (50): 12099. doi:10.1002/anie.201105081. 15. ^ D. Ajami, O. Oeckler, A. Simon, R. Herges (2003). "Synthesis of a Mbius aromatic hydrocarbon". Nature 426 (6968): 81921. doi:10.1038/nature02224. PMID 14685233. 16. ^ Claire Castro, Zhongfang Chen, Chaitanya S. Wannere, Haijun Jiao, William L. Karney, Michael Mauksch, Ralph Puchta, Nico J. R. van Eikema Hommes, Paul von R. Schleyer (2005). "Investigation of a Putative Mbius Aromatic Hydrocarbon. The Effect of Benzannelation on Mbius [4 n]Annulene Aromaticity". J. Am. Chem. Soc. 127 (8): 24252432. doi:10.1021/ja0458165.
17. ^ Rzepa, Henry S. (2005). "A Double-Twist Mbius-Aromatic Conformation of [14]Annulene". Organic Letters 7 (21): 46379. doi:10.1021/ol0518333. PMID 16209498.