Aromatic molecular orbital

Pyrrole, furan, and thiophene give electrophilic substitution products because they re aromatic (Section 15.7). Each has six -ir electrons in a cyclic conjugated system of overlapping p orbitals. Taking pyrrole as an example, each of the four carbon atoms of pyrrole contributes one n electron, and the sp -hybridized nitrogen atom contributes two (its lone pair). The six ir electrons occupy p orbitals, with lobes above and below the plane of the ring, as shown in Figure 28.1. Overlap of the five p orbitals forms aromatic molecular orbitals just as in benzene. 

The rule fails trivially for all complexes of saturated ligands (PH3 may be considered as unsaturated because of its empty 3d orbitals), even where the 18-electron rule is obeyed, since there is no possibility of back-bonding in these cases. It also fails for (C6H6)2Cr, where the d(xy, x —y ) are used in back-bonding, but the d(z ) (or d(z )—s hybrid) is either totally non-bonding or else feebly antibonding to the lowest aromatic molecular orbital of the rings. 

Key words Aromaticity - Molecular orbital theory -Valence bond theory... 

Pierrefixe SCAH, Bickelhaupt EM (2007) Aromaticity molecular-orbital picture of an intuitive concept. Chem Eur J 13 6321-6328... 

HMO theory is named after its developer, Erich Huckel (1896-1980), who published his theory in 1930 [9] partly in order to explain the unusual stability of benzene and other aromatic compounds. Given that digital computers had not yet been invented and that all Hiickel s calculations had to be done by hand, HMO theory necessarily includes many approximations. The first is that only the jr-molecular orbitals of the molecule are considered. This implies that the entire molecular structure is planar (because then a plane of symmetry separates the r-orbitals, which are antisymmetric with respect to this plane, from all others). It also means that only one atomic orbital must be considered for each atom in the r-system (the p-orbital that is antisymmetric with respect to the plane of the molecule) and none at all for atoms (such as hydrogen) that are not involved in the r-system. Huckel then used the technique known as linear combination of atomic orbitals (LCAO) to build these atomic orbitals up into molecular orbitals. This is illustrated in Figure 7-18 for ethylene. 

The electronic theory of organic chemistry, and other developments such as resonance theory, and parallel developments in molecular orbital theory relating to aromatic reactivity have been described frequently. A general discussion here would be superfluous at the appropriate point a brief summary of the ideas used in this book will be given ( 7- )-... 

FIGURE 11 10 The lowest energy tt molecular orbital of benzyl radical shows the interaction of the 2p orbital of the benzylic carbon with the TT system of the aromatic ring... 

Cyclic conjugation although necessary for aromaticity is not sufficient for it Some other factor or factors must contribute to the special stability of benzene and compounds based on the benzene ring To understand these factors let s return to the molecular orbital description of benzene... 

One of molecular orbital theories early successes came m 1931 when Erich Huckel dis covered an interesting pattern m 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 Huckel found that whether a hydrocarbon of this type was aromatic depended on its number of tt electrons He set forth what we now call Huckel s rule... 

Electrophilic Aromatic Substitution. The Tt-excessive character of the pyrrole ring makes the indole ring susceptible to electrophilic attack. The reactivity is greater at the 3-position than at the 2-position. This reactivity pattern is suggested both by electron density distributions calculated by molecular orbital methods and by the relative energies of the intermediates for electrophilic substitution, as represented by the protonated stmctures (7a) and (7b). Stmcture (7b) is more favorable than (7a) because it retains the ben2enoid character of the carbocycHc ring (12). 

Aromatic Radical Anions. Many aromatic hydrocarbons react with alkaU metals in polar aprotic solvents to form stable solutions of the corresponding radical anions as shown in equation 8 (3,20). These solutions can be analyzed by uv-visible spectroscopy and stored for further use. The unpaired electron is added to the lowest unoccupied molecular orbital of the aromatic hydrocarbon and a... 

A number of derivatives of antimonin are also known (141,142). The potential aromaticity of this ring system has aroused considerable interest and has been investigated with the aid of spectroscopy as well as ab initio molecular orbital calculations (143). There seems to be no doubt that antimonin does possess considerable aromatic character. 

Aromaticity is usually described in MO terminology. Cyclic structures that have a particularly stable arrangement of occupied 7t molecular orbitals are called aromatic. A simple expression of the relationship between an MO description of stmcture and aromaticity is known as the Hiickel rule. It is derived from Huckel molecular orbital (HMO) theory and states that planar monocyclic completely conjugated hydrocarbons will be aromatic when the ring contains 4n + 2 n electrons. HMO calculations assign the n-orbital energies of the cyclic unsaturated systems of ring size 3-9 as shown in Fig. 9.1. (See Chapter 1, Section 1.4, p. 31, to review HMO theory.)... 

Bicyclo[6.2.0]deca-2,4,6,8,10-pentaene has been synthesized, and a number of molecular orbital and molecular mechanics calculations have been performed to determine whether it is aromatic or antiaromatic. Consider the structure and discuss the following points. 

Figure 11.14 shows a molecular orbital diagrfflTt for cycloheptatrienyl cation. There are seven tt MOs, three of which are bonding and contain the six tt electrons of the cation. Cycloheptatrienyl cation is a Hiickel (4n + 2) system and is an aromatic ion. 

Paradoxically, although they are electron-rich, S-N compounds are good electron acceptors because the lowest unoccupied molecular orbitals (LUMOs) are low-lying relative to those in the analogous carbon systems. For example, the ten r-electron [SsNs] anion undergoes a two-electron electrochemical reduction to form the trianion [SsNs] whereas benzene, the aromatic hydrocarbon analogue of [SsNs], forms the monoanion radical [CeHg] upon reduction. ... 

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