Relative reactivities, qualitative evaluation

Consequently, with the present knowledge of reductive dehalogenation reactions of Cr and C2-compounds, and considering the quality of the various molecular descriptors, only qualitative, or at most semiquantitative, predictions of the relative reactivities of a confined set of structurally related compounds in a given system are possible. Nevertheless, evaluation of such relative reactivities in different systems may provide important insights into such reactions, which will be demonstrated by the following two examples. These two examples will, however, also illustrate the... 

Reactivity is a qualitative, general and relative term, similar to acidity or basicity. It can be quantitatively expressed by the value of rate constant in the corresponding reaction of the evaluated component with a partner in a given medium. 

DFT can evaluate properties and mutual reactivity from the electron distribution. These relationships between qualitative concepts in chemistry, such as electronegativity and polarizability, suggest that DFT does incorporate fundamental relationships between molecular properties and structure. At this point, we want to emphasize the conceptual relationships between the electron density and electronegativity and polarizability. We can expect electrophiles to attack positions with relatively high electron density and polarizability. Nucleophiles should attack positions of relatively... 

To end this overview, let me say a few words about the likely evolution of the calculations devoted to theoretically analyze the stability and reactivity of cyclodextrin complexes. Hybrid methods have recently opened the door for the most sophisticated ab initio and DFT methods to deal with molecular systems with hundreds or even thousands of atoms if the reactive center is well localized within a particular zone of the whole macromolecular system. As computers keep on growing in capacity and theoretical methods are progressively more well established, theoretical work on host guest complexes will be ready to make a jump from the qualitative predictions, already available now, to the quantitative results. This will provide a powerful tool for the experiments as theory will be helpful not just to explain reactions already known but to predict new reactions and effects of the supramolecular environment that have been until now out of reach of precise measurements (as intermolecular forces are quite tenuous, their theoretical evaluation is subject to noticeable relative errors). On the other hand, it is to be noted that electronic calculations alone are not able to disclose the rich molecular dynamics of such a large molecular systems. Up to now MC and MD procedures have been restricted to find the more stable conformations but they are able to tell us more details about the mechanism of the inclusion process and reactivity inside CD and other large guests. The applicability of these methods to such problems has also been... 

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