Quantitative representation of reactivity, selectivity and site activation concepts in organic chemistry
Contreras, Renato R.
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Reactivity, selectivity and site activation are classical concepts in chemistry which are amenable to quantitative representation, in terms of static global, local and non local density response functions. The use of these electronic indexes describing chemical interconversion is developed in this work along the perspective of the pioneering work conducted in Chile by the late Professor Fernando Zuloaga, to whom this article is dedicated in memoriam. While global responses, represented as derivatives of the electronic energy with respect to the total number of electrons quantitatively describe the propensity of a system to interconvert into another chemical species (chemical reactivity), the local counterparts assesses well those regions in the molecule where the reactivity pattern dictated by the global quantities is developed (selectivity). Site activation /deactivation may in turn be described by the variations in the local or regional patterns of reactivity, that may be induced by solvent effects or chemical substitution. These concepts are illustrated for a series of chemical reactions in Organic Chemistry, including electrocyclic processes, cycloadditions and electrophilic addition reactions. Some relationships between quantitative scales of reactivity and reaction mechanisms are discussed.