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By David Ginsburg (auth.)

Content material: Of propellanes - and of spirans / D. Ginsburg -- a brand new therapy of chemical reactivity / J. Gasteiger ... [et al.] -- Transition-metal catalyzed decomposition of aliphatic diazo compounds - new effects and purposes in natural synthesis / G. Maas

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The Allen scheme 26) was chosen as a reasonable compromize between the number of parameters and estimation accuracy. Parameters for each molecule are assigned to 1,2-interactions (bonds) and those 1,3-interactions not involving hydrogen atoms. This scheme is numerically equivalent to the widely used Benson group additivity scheme 27~ but offers advantages over the lat/~er for our purposes. An increase in the accuracy of the 38 A New Treatment of Chemical Reactivity estimate has been achieved 2s.

An iterative procedure was developed to quantify this Partial Equalization of Orbital Eleetronegativities (PEOE) 4°'41). The form of the algorithm ensures rapid convergence. Consideration of changes in hybridization enables the peculiar bonding situations encountered in systems containing three- and four-membered rings to be calculated 42). The conceptual basis of the PEOE procedure has been analyzed and compared with other definitions of eleetronegativity ,3) As there is no unambiguous definition of partial atomic charges, a host of physical data was investigated to show the utility of the charge values.

Chemical reactions, since no predictions of the energies of transition states can be made. However, it provides a powerful means lbr determining the thermochemical framework within which the actual course of a reaction has to be searched. The values of reaction enthalpies in a forward search can be of use in predicting the products of a reaction: the more exothermic a reaction, the more it should be preferred. The situation will be different in a retrosynthetic search where retroreactions should be calculated to be endothermic to some degree.

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