Benzene and Other Aromatic Compounds
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If benzene is forced to react by increasing the temperature and/or by addition of a catalyst, It undergoes substitution reactions rather than the addition reactions that are typical of alkenes. This further confirms the previous indication that the six-carbon benzene core is unusually stable to chemical modification. The conceptual contradiction presented by a high degree of unsaturation (low H:C ratio) and high chemical stability for benzene and related compounds remained an unsolved puzzle for many years. Eventually, the presently accepted structure of a regular-hexagonal, planar ring of carbons was adopted, and the exceptional thermodynamic and chemical stability of this system was attributed to resonance stabilization of a conjugated cyclic triene.
Here, two structurally and energetically equivalent electronic structures for a stable compound are written, but no single structure provides an accurate or even an adequaterepresentation of the true molecule.
The six-membered ring in benzene is a perfect hexagon (all carbon-carbon bonds have an identical length of 1.40 Å). The cyclohexatriene contributors would be expected to show alternating bond lengths, the double bonds being shorter (1.34 Å) than the single bonds (1.54 Å). An alternative representation for benzene (circle within a hexagon) emphasizes the pi-electron delocalization in this molecule, and has the advantage of being a single diagram. In cases such as these, the electron delocalization described by resonance enhances the stability of the molecules, and compounds composed of such molecules often show exceptional stability and related properties.
Evidence for the enhanced thermodynamic stability of benzene was obtained from measurements of the heat released when double bonds in a six-carbon ring are hydrogenated (hydrogen is added catalytically) to give cyclohexane as a common product. In the following diagram cyclohexane represents a low-energy reference point. Addition of hydrogen to cyclohexene produces cyclohexane and releases heat amounting to 28.6 kcal per mole. If we take this value to represent the energy cost of introducing one double bond into a six-carbon ring, we would expect a cyclohexadiene to release 57.2 kcal per mole on complete hydrogenation, and 1,3,5-cyclohexatriene to release 85.8 kcal per mole. These heats of hydrogenation would reflect the relative thermodynamic stability of the compounds. In practice, 1,3-cyclohexadiene is slightly more stable than expected, by about 2 kcal, presumably due to conjugation of the double bonds. Benzene, however, is an extraordinary 36 kcal/mole more stable than expected. This sort of stability enhancement is now accepted as a characteristic of all aromatic compounds.
A molecular orbital description of benzene provides a more satisfying and more general treatment of "aromaticity". We know that benzene has a planar hexagonal structure in which all the carbon atoms are sp2 hybridized, and all the carbon-carbon bonds are equal in length. As shown below, the remaining cyclic array of six p-orbitals ( one on each carbon) overlap to generate six molecular orbitals, three bonding and three antibonding. The plus and minus signs shown in the diagram do not represent electrostatic charge, but refer to phase signs in the equations that describe these orbitals (in the diagram the phases are also color coded). When the phases correspond, the orbitals overlap to generate a common region of like phase, with those orbitals having the greatest overlap (e.g. π1) being lowest in energy. The remaining carbon valence electrons then occupy these molecular orbitals in pairs, resulting in a fully occupied (6 electrons) set of bonding molecular orbitals. It is this completely filled set of bonding orbitals, or closed shell, that gives the benzene ring its thermodynamic and chemical stability, just as a filled valence shell octet confers stability on the inert gases.
The Molecular Orbitals of Benzene
- William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry