Dewar’s reactivity number

Somewhat more involved is the computation of further reactivity indices Wheland s atom localization energy, A6 exact super-delocalizability, S7 various polarizabilities, ir8 Brown s factor, Z° Dewar s reactivity number, Ap10 and the approximate superdelocali-zability, S 7... 

Dewar s treatment of transition state structure, using reactivity numbers, has the logical defect that in the intermediate kinds of transition states for which it provides evidence the electron localisation is only partial. However, in obtaining the values of the reactivity numbers (which are approximate localization energies), the process of localization is considered to be complete thus, values of parameters which strictly are relevant only to the Wheland type of transition state are incorporated into a different model. ... 

Various reactivity indices have been derived for benzenoid hydrocarbons from the following purely topological approaches the Huckel model (HMO), first-order perturbation theory (PMO), the free electron MO model (FEMO), and valence-bond structure resonance theory (VBSRT). Since many of the indices that have been known for a long time (index of free valence Fr, self-atom polarizability ir , superdelocalizability Sr, Brown s index Z, cation localization energy Lr+, Dewar reactivity number Nt, Brown s para-localization energy Lp) have been described in detail by Streitwieser in his well-known volume [23] we will refer here only to some more recent developments. 

Experimental log k2 values were correlated with Brown para-localization energies, Dewar reactivity numbers, Herndon structure count ratios, Hess-Schaad resonance energy differences, indices of free valence, and second-order perturbation stabilization energies. The latter are based on Fukui s frontier orbital theory [67] which classifies the Diels-Alder reaction of benzenoid hydrocarbons with maleic anhydride as mainly HOMO (aromatic hydrocarbon)-LUMO (maleic anhydride) controlled. However, the corresponding orbital interaction energy given by... 

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