Aromaticity bond orbital atomic charges

The relative Michael-acceptor abilities of a variety of substituted aromatic and aliphatic nitroalkenes have been elucidated by computational methods. Several global and local reactivity indices were evaluated with the incorporation of the natural charge obtained from natural bond orbital (NBO) analysis. Natural charges at the carbon atom to the NO2 group and the condensed Fukui functions derived by this method were found to be consistent with the reactivity.187... 

One may therefore tentatively conclude from this, in the case of a [2 + 2] cycloaddition or reversion, that a diradical transition state is most likely, if it is stabilized by substituents in the 2,5-position by means of a mesomeric interaction. Otherwise the equilibrium is shifted to the tetraphosphahexadiene. This explains the observations with respect to the reaction proceeding and hence the influence of the substituents at the two carbon atoms. If, in the case of a hindered orbital overlap between the substituents and the PC double bonds, a quasiaromatic interaction is blocked, the equilibrium is shifted to the tetraphosphahexadiene. On the other hand, if substituents in the 2,5-position are able to interact with the PC double bond, a mesomeric charge transfer into the side chain takes place, obstructing the aromatic transition state and so favoring the 1,4-cyclohexadiyl radical, which recombines to the bicyclic compound (Fig. 8). The carbon atom and its substituents... 

Chemical bonds together with other concepts such as atomic orbitals, electron shells, lone pairs, aromaticity, atomic charges, (hyper-) conjugation, strain, etc. do not correspond to physical observables. Such concepts therefore cannot be unambiguously defined in pure quantum theory, but constitute a rich set of fuzzy , yet invaluably useful concepts [11-14]. They lead to constmctive ideas and developments when appropriately used and defined. 

Aromatic substitution reactions are often complicated and multistep processes. A correlation, however, in many cases can be found between the charged attacking species and the electron density distribution in the molecule attacked during electrophilic and nucleoph c substitution. No such correlation is expected in radical substitution where the attacking particles are neutral, rather a correlation between the reactivities of separate bonds and a free valency index of the bond order. This allows the prediction of the most reactive bonds. Such an approach has been used by researchers who applied quantum calculations to estimate the reactivities of the isomeric thienothiophenes and to compare them with thiophene or naphthalene. " Until recently quantum methods for studying reactivities of aromatics and heteroaromatics were developed mainly in the r-electron approximation (see, for example, Streitwieser and Zahradnik ). The M orbitals of a sulfur atom were shown not to contribute substantially to calculations of dipole moments, polarographic reduction potentials, spin-density distribution, ... 

On the basis of Hiickel s An +2) n- electron rule, all of these systems can be expected to be aromatic in nature. They do indeed exhibit varying degrees of aromatic stabilization depending on the nature and position of the heteroatom. They cannot all be represented by conventional classical structures. Structures (la)-(lc) can be represented by classical covalent bonded structures whereas those of the (Id) type form the nonclassical structures in the sense that they can be drawn only as charge-separated systems or biradicals in systems wherein X/Y are sulfur or selenium atoms, d- orbital participation in bonding is conceivable, leading to tetravalent sulfur or selenium. 

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